Basic magnesium salts processes and lubricants and fuels containing the same

ABSTRACT

PROCESSES FOR PREPARING BASIC MAGNESIUM SALTS OF OIL SOLUBLE ORGANIC ACIDS BY CONTACTING AN INORGANIC ACIDIC MATERIAL WITH A MIXTURE OF THE ACIDS, OR THEIR ALKALI OR ALKALINE EARTH METAL SALTS, MAGNESIUM OXIDE, AND WATER OR ALCOHOL-WATER PROMOTER SYSTEM. CARBON DIOXIDE IS AN EXEMPLARY ACIDIC MATERIAL. LOWER ALKANOLS PARTICULARLY METHANOL, ARE USEFUL CO-PROMOTERS FOR USE WITH THE WATER. MIXTURES OF OIL-SOLUBLE SULFONIC ACIDS AND OIL-SOLUBLE CARBOXYLIC ACIDS, OR THEIR ALKALI OR ALKALINE EARTH METAL SALTS, ARE USEFUL STARTING MATERIALS FOR PREPARING BASIC MAGNESIUM SALTS. WITH ALCOHOL-WATER CO-PROMOTERS, THE INORGANIC ACIDIC MATERIAL IS CONTACTED WITH THE REACTION MIXTURE IN TWO STAGES, FIRST IN THE PRESENCE OF BOTH PROMOTERS AND THEN IN THE PRESENCE OF WATER ONLY. THE PRODUCTS ARE USEFUL AS ADDITIVES IN LUBRICANTS AND FUELS AND AS INTERMEDIATES IN PREPARING OTHER USEFUL PRODUCTS.

United States Patent Olhce 3,629,109 Patented Dec. 21, 1971 US. Cl.252-33 50 Claims ABSTRACT OF THE DISCLOSURE Processes for preparingbasic magnesium salts of oil soluble organic acids by contacting aninorganic acidic material with a mixture of the acids, or their alkalior alkaline earth metal salts, magnesium oxide, and water oralcohol-water promoter system. Carbon dioxide is an exemplary acidicmaterial. Lower alkanols, particularly methanol, are useful co-promotersfor use with the water. Mixtures of oil-soluble sulfonic acids andoil-soluble carboxylic acids, or their alkali or alkaline earth metalsalts, are useful starting materials for preparing basic magnesiumsalts. With alcohol-water co-promoters, the inorganic acidic material iscontacted with the reaction mixture in two stages, first in the presenceof both pro motors and then in the presence of water only. The productsare useful as additives in lubricants and fuels and as intermediates inpreparing other useful products.

This is a continuation-in-part application of copending application Ser.No. 785,343 filed Dec. 19, 1968, now abandoned.

This invention relates to basic, oil-soluble magnesium salts of organicacids, processes for preparing such basic salts and to lubricatingcompositions containing these basic magnesium salts. More particularly,the invention is concerned with basic magnesium salts of organic acidsprepared by a process which comprises contacting at least one acidicmaterial with at least one oil-soluble organic acid or suitablederivative thereof and at least one basically reacting magnesiumcompound in the presence of water or a combination of at least onealcohol and water.

As is well-known, basic magnesium salts of organic acids are known inthe art and have been utilized as additives for lubricants and fuels.For example, basic magnesium salts, processes for their preparation, anddiscussion of their usefulness as additives in lubricants and fuels isfound in such prior U.S. Pats. as 2,585,520; 2,739,124; 2,889,279;2,895,913; 3,149,074; 3,150,089; and 3,235,494. However, as recounted inUS. Pat. 3,150,089, those skilled in the art have sought improved oralternative methods for preparing basic magnesium salts. Those processeswhich have been developed for the preparation of basic barium andcalcium salts have not been entirely satisfactory when used in thepreparation of basic magnesium salts. Furthermore, many of the prior artprocesses invloved the use of magnesium metal as an intermediate in thepreparation of magnesium alkoxides and the use of metallic magnesium hasobvious drawbacks.

It has now been determined that basic magnesium salts of organic acidscan be readily perpared by contacting certain acidic materials withcertain organic acids or salts thereof with active magnesium oxide inthe presence of water or a water-alcohol promoter system. It has alsobeen found that higher metal ratios can be achieved if the acidicmaterial is contacted with the reaction mixture in two steps; i.e., inthe presence of both an alcohol and water, subsequently removing anyfree alcohol from the mixture, and continuing contacting of the acidicmaterial with the remainder of the reaction mixture in the presence ofwater as the only promoter. Furthermore, the use of oil-solublealiphatic carboxylic acids or equivalent derivatives thereof incombination with the other organic acids susceptible to overbasingresults in an advantageous process and novel products. These processes,the novel basic magnesium salts produced according thereto, andlubricating and fuel compositions containing basic salts produced bythese processes are contemplated as being within the scope of thepresent invention.

In accordance with the foregoing, it is a principal object of thisinvention to provide novel basic, oil-soluble magnesium salts of organicacids including basic magnesium salts having metal ratios of up to about30 or even higher. A further major object is to provide new processesfor preparing basic, oil-soluble magnesium salts of organic acids. Afurther principal object of the invention is to provide fuel orlubricating compositions comprising respectively, a major amount of anormally liquid fuel or lubricant base and a minor amount of a basic,oil-soluble magnesium salt of an organic acid prepared according to aprocess of this invention. An additional object of the invention is toprovide a process for preparing basic magnesium salts utilizing water oralcohol combinations as the promoter system. Another object of theinvention is to provide basic, carbonated, oil-soluble magnesium saltsof a combination of at least one oil-soluble sulfonic acid and at leastone oil-soluble aliphatic carboxylic acid through a process comprisingcarbonating the mixture of said acids in the presence of methanol andwater, removing the methanol, and continuing carbonation. Still an otherobject of this invention is to provide lubricant compositions comprisinga major amount of a lubricating oil and a minor amount of a basic,oil-soluble magnesium salt prepared according to the present invention.A further object is to provide concentrates containing the novel basicmagnesium salts prepared according to the process of the presentinvention, for example, lubricating oil compositions containing thesebasic magnesium salts in amounts such that when they are incorporatedinto larger quantities of lubricating oil to prepare lubricating compositions, the lubricating composition will contain a sufiicientquantity of the basic magnesium salts to provide detergency to saidcomposition, alone or with other detergents or dispersants.

These and other objects of this invention are achieved by providing aprocess for preparing oil-soluble basic magnesium salts comprisingintimately contacting an acidic material with a mixture comprising (a)at least one member selected from oil-soluble organic acids and theirequivalent derivatives susceptible to overbasing (b) a stoichiometricexcess based on the total equivalents of acid in (a) of a basicallyreacting magnesium compound and (c) water. The novel basic magnesiumsalts of organic acids contemplated as being within the ambit of thepresent invention are those which are produced in accordance with thisgeneral process while the fuel and lubricating compositions contemplatedare those containing such basic magnesium salts.

In a more preferred aspect of the invention, the foregoing objectivesare achieved by providing a process for preparing oil-soluble,carbonated, basic magnesium salts comprising carbonating a mixturecomprising (a) X equivalents of at least one member selected fromoil-soluble organic acids and alkali or alkaline earth metal saltsthereof, (b) Y equivalents of at least one oil-soluble aliphaticcarboxylic acid alkali or alkaline earth metal salts thereof includingmagnesium salts, (e) Z equivalents of magnesium oxide wherein the valueof is from about 1.1 to about 30 or more but usually up to about 20, (d)at least one lower aliphatic alcohol having up to seven carbon atoms,(e) water and (f) a substantially inert organic liquid medium comprisingmineral oil and at least one additional substantially inert organicliquid having a lower boiling point than said mineral oil but higherthan water, until the reaction between the carbon dioxide and themixture substantially ceases, subsequently removing substantially allthe free lower aliphatic alcohol, while continuing carbonation until theliquid phase of the carbonated mixture is substantially clear and easilyfilterable. The ratio of X :Y is generally about 1:1 to about 20: 1. Thelower alkanols, especially alkanols selected from the class consistingof methanol or mixtures of methanol and at least one additional loweralkanol are preferred for this aspect of the invention. Basic magnesiumsalts thus produced and lubricating compositions and concentratescontaining such salts constitute preferred embodiments of the invention.

As used in the present specification, a basic salt iS one characterizedby the presence of a stoichiometric excess of metal relative to thenumber of equivalents of oilsoluble organic acid present therein basedon the normal stoichiometry of the particular metal and organic acids.For example, a neutral or normal organic acid salt of magnesium ischaracterized by an equivalent ratio of magnesium to acid of 1:1, whilea basic salt is characterized by a higher ratio, e.g., 1.1:1, 2:1, 5:1,:1, :1, :1, :1, etc. The term metal ratio is used to designate the ratioof equivalents of metal to acid in a basic salt to the number ofequivalents expected to be present in a normal salt based on the usualstoichiometry of the metal or metals involved and the organic acid oracids present. Thus, an oil-solution of a basic magnesium saltcontaining one equivalent of an oil-soluble sulfonic acid, oneequivalent of an oil-soluble carboxylic acid, and twenty equivalents ofmagnesium would have a metal ratio of 20+(l+1) or 10. Likewise, anoil-solution of a basic salt characterized by the presence of twoequivalents of a petrosulfonic acid, one equivalent of isostearic acid,three equivalents of calcium, and fifteen equivalents of magnesium has ametal ratio of (3+15)+(2-]-l) or 6.

In the present specification, magnesium is regarded as an alkaline earthmetal and as having two equivalents per atomic weight; magnesium oxide(MgO) and magnesium hydroxide, two equivalents per mole; etc. Theoil-soluble organic acids are regarded as having one equivalent of acidper acidic hydrogen or acid group. Thus, a monocarboxylic acid ormonosulfonic acid or their equivalent derivatives such as esters andammonium and metal salts have one equivalent per mole of acid; ester, orsalt; a disulfonic acid or dicarboxylic acid or equivalent derivativehas two equivalents per mole, etc. Basically reacting alkali metalcompounds such as sodium hydroxide have one equivalent per mole (moreaccurately, one equivalent per atomic weight of metal). The basicallyreacting alkaline earth metal compounds such as the oxides, hydroxides,carbonates, and alkoxides (e.g., calcium oxide, calcium hydroxide,barium oxide, barium hydroxide, strontium hydroxide, calcium carbonate,calcium methoxide, barium isopropoxide, etc.), have two equivalents permole (i.e., two equivalents per atomic weight of metal).

Metal salts of acids characterized by metal ratios in excess of one havebeen referred to in the prior art as basic salts, complex salts,superbased salts, overbased salts, and the like. Herein, the terminologybasic salts is employed. The processes for making such salts arereferred to as overbasing processes. The exact nature of basic salts isnot understood. It has been suggested by some that they comprise stabledispersions of salts formed by contacting the acidic material with thebasically reacting metal compounds. Others regard them as polymericsalts formed by the reaction of the acidic material, the acid beingoverbased, and the basically reacting metal compound (see, for example,German Auslegeschrift 1,243,915). For this reason, the salts aredescribed herein mainly by reference to the processes by which they areproduced.

The acidic materials which can be used in the processes of the presentinvention include inorganic acids, usually acidic gases or liquids, suchas H ,BO CO H S, S0 HCl, N0 PO1 C10 SOCI B1 CS COS, etc. Lower aliphaticcarboxylic acids can also be used, e.g., oxalic, acetic, propionicacids, and the like. Formic acid is the preferred carboxylic acid.However, the inorganic acidic gases, particularly, CO S0 and H 5 areparticularly preferred. Carbon dioxide is the most preferred inorganicacidic material due to overall considerations of cost, ease of use,availability, and performance of the resulting products.

Organic acids susceptible to overbasing, that is, those which can beconverted to basic magnesium salts according to the present inventioninclude those known organic acids which have been used or are presentlyused in preparing basic alkaline earth metal salts (e.g., thosedescribed in US. Pats. 3,312,618; 2,695,910; and 2,616,904) andconstitute an art-recognized class of acids. These organic acids aregenerally oil-soluble acids but oilinsoluble organic acids can be usedin the present process provided basic magnesium salts prepared therefromaccording to the procedures of the present invention are soluble in oils(including fuels, fuel oils) at a concentration at which the basicmagnesium salt imparts desirable properties thereto as described herein.Thus in the present specification organic acids can be consideredoil-soluble if they or their normal or basic metal salts areoil-soluble. The phosphorus acids, carboxylic acids, and sulfur acids,which are oil-soluble per se, particularly the oil-soluble sulfonicacids, are especially useful. Oil-soluble derivatives of these organicacids susceptible to overbasing such as their metal salts (e.g., Group Iand Group II normal and basic metal salts) ammonium salts, and esters(particularly esters with lower aliphatic alcohols having up to sixcarbon atoms such as the lower alkanols), can be utilized in the presentprocesses in lieu of or in combination with the free acids. The alkalimetal-salts can, if desired, be converted in situ to the magnesium orother alkaline earth metal salt by conventional double decompositiontechniques. When reference is made to the acid, its equivalentderivatives susceptible to overbasing are implicitly included unless itis clear that only the acid is intended. Preferably, an oil-solubleorganic acid or its oil-soluble neutral or basic alkali or alkalineearth metal salts, including magnesium salts, or mixtures of these willbe employed as the oil-soluble organic acid reactant in the processes ofthis invention.

The phosphorus-containing acids are characterized by at least oneoil-solubilizing group attached directly to phosphorus via a carbonatom, e.g., oil-soluble phosphinic and phosphonic acids including theoil-soluble thiophosphinic and thiophosphonic acids. Preferredphosphorus acids are those prepared by reacting olefins with phosphorussulfides (e.g., phosphorus pentasulfide). Steamtreated reaction productsof phosphorus pentasulfide and polyolefins such as polyisobutylene andpolypropylene are particularly useful. Such acids are well-known asshown by US. Pats. 2,316,078; 2,316,080; 2,316,091; 2,367,468;2,375,315; 2,377,955; 2,496,508; 2,507,731; 2,516,119; 2,597,750;2,647,889; 2,688,612; and 2,915,517 which describe the preparation ofmetal salts of the acids and the preparation of the acid intermediates.

Suitable carboxylic acids include aliphatic, cycloali phatic, andaromatic mono and polybasic carboxylic acids such as the naphtheticacids, alkylor alkenyl-substituted cyclopentanoic acids, alkyloralkenyl-substituted cyclohexanoic acids, alkylor alkenyl-substitutedaromatic carboxylic acids. The aliphatic acids generally contain atleast eight carbon atoms and preferably at least twelve carbon atoms.Generally, if the aliphatic carbon chain is branched, the acids are moreoil-soluble for any given carbon atom content. The cycloaliphatic andaliphatic carboxylic acids can be saturated or unsaturated. Specificexamples include 2-ethylhexanoic acid, a-linolenic acid,propylene-tetramer-substituted maleic acid, behenic acid, isostearicacid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid,lauric acid, oleic acid, ricinoleic acid, undecylic acid,dioctyldyclopentane carboxylic acid, myristic acid,dilauryldecahydronaphthalene carboxylic acid, stearyl-octahydroindenecarboxylic acid, palmitic acid, commercially available mixtures of twoor more carboxylic acids such as tall oil acids, rosein acids, and thelike.

A preferred group of oil-soluble carboxylic acids useful in preparingthe basic magnesium salts of the present invention are the oil-solublearomatic carboxylic acids. These acids are represented by the generalformula:

where R is a hydrocarbon or essentially hydrocarbon radical containingat least four aliphatic carbon atoms, n is an integer of from one tofour, Ar is a polyvalent aromatic hydrocarbon radical having a total of.up to fourteen carbon atoms in the aromatic nucleus, each X isindependently a divalent sulfur or oxygen group, and m is an integer offrom one to four with the proviso that R and n are such that there is anaverage of at least eight aliphatic carbon atoms provided by the Rsubstituents for each acid molecule represented by Formula I. Examplesof aromatic radicals represented by' the variable Ar are the polyvalentaromatic radicals derived from benzene, naphthalene, anthracene,phenanthrene, indene, fluorene, biphenyl, and the like. Generally, theradical represented by Ar will be a polyvalent radical derived frombenzene or naphthalene such as phenylenes and naphthylene, e.g.,methylphenylenes, ethoxyphenylenes, nitrophenylenes,isopropylphenylenes, hydroxyphenylenes, mercaptophenylenes,N,N-diethylaminophenylenes, chlorophenylenes, dipropoxynaphthylenes,triethylnaphthylenes, and similar tri-, tetra-, pentavalent radicalsthereof, etc.

The R variables are usually hydrocarbon groups, preferably aliphatichydrocarbon groups such as alkyl or alkenyl radicals. However, the Rgroups can contain such substituents as phenyl, cycloalkyl (e.g.,cyclohexyl, cyclopentyl, etc.) and nonhydrocarbon groups such as nitro,amino, halo (e.g., chloro, bromo, etc.), lower alkoxy, lower alkylmercapto, oxo substituents (i.e.,=O), thio groups (i.e.,=S),interrupting groups such as NH, O, S, and the like provided theessentially hydrocarbon character of the R variable is retained. Thehydrocarbon character is retained for purposes of this invention so longas any non-carbon atoms present in the R variables do not account formore than about of the total weight of the R variables. Examples of Rgroups include butyl, isobutyl, pentyl, octyl, nonyl, dodecyl, docosyl,tetracontyl, S-chlorohexyl, 4-ethoxypentyl, 4- hexenyl,3-cyclohexyloctyl, 4-(p-ch1orophenyl) octyl, 2,3,S-trimethylheptyl,4-ethyl-5-methyloctyl, and substituents derived from polymerized olefinssuch as polychloroprenes, polyethylenes, propypropylenes,polyisobutylenes, ethylene-propylene copolymers, chlorinated olefinpolymers, oxidized ethylene-propylene copolymers, and the like. Likewisethe variable Ar may contain nonhydrocarbon substituents, for example,such diverse substituents as lower alkoxy, lower alkyl mercapto, nitro,halo, alkyl or alkenyl groups of less than four carbon atoms, hydroxy,mercapto, and the like.

where R, X, Ar, m and n are as defined in Formula I and p is an integerof 1 to 4, usually 1 or 2. Within this group, an especially preferredclass of oil-soluble carboxylic acids are those of the formula:

where R is an aliphatic hydrocarbon radical containing at least fourcarbon atoms, a is an integer of from 1 to 3, b is 1 or 2, c is zero, 1,or 2 and preferably 1 with the proviso that R and a are such that theacid molecules contain at least an average of about twelve aliphaticcarbon atoms in the aliphatic hydrocarbon substituents per acidmolecule. And within this latter group of oilsoluble carboxylic acids,the aliphatic-hydrocarbon substituted salicylic acids wherein eachaliphatic hydrocarbon substituent contains an average of at least aboutsixteen carbon atoms per substituent and one to three substituents permolecule are particularly useful. Basic magnesium salts prepared fromsuch salicylic acids wherein the aliphatic hydrocarbon substituents arederived from polymerized olefins, particularly polymerized lowerl-monoolefins such as polyethylene, polypropylene, polyisobutylene,ethylenepolypropylene copolymers and the like and having an averagemolecular weight of about 200 to about 1200, preferably about 300 toabout 700, are very useful as lubricant additives.

The oil-soluble carboxylic acids corresponding to Formulae I-III aboveare well-known or can be prepared according to procedures known in theart. Carboxylic acids of the type illustrated by the above formulae andprocesses for preparing their metal salts are disclosed in such U.S.Pats. are 2,197,832; 2,197,835; 2,252,662; 2,252,664; and 2,714,092. Thesalts can be converted to the acid by neutralizing with an inorganicacid such as HCl.

The most preferred oil-soluble organic acids for use in preparing thebasic magnesium salts are the oil-soluble sulfonic acids including thesynthetic oil-soluble sulfonic acids. Suitable oil-soluble sulfonicacids are represented by the general formulae:

In Formula 1V, T is a cyclic nucleus of the monoor polynuclear typeincluding benzenoid or heterocyclic neuclei such as a benzene,naphthalene, anthracene, 1,2,3,4-tetrahydronaphthalene, thianthrene, orbiphenylnucleus and the like. Ordinarily, however, T will represent anaromatic hydrocarbon nucleus, especially a benzene or naphthalenenucleus. The variable R in the radical R includes the same groups as theR variable in Formula I above and can be, for example, an aliphaticgroup such as alkyl, alkenyl, alkoxy, alkoxyalkyl, carboalkoxyalkyl, anaralkyl group, or other hydrocarbon or essentially hydrocarbon groups,while x is at least one with the proviso that the variables representedby the group R are such that the acids are oil-soluble. This means thatthe groups represented by R should contain at least about eightaliphatic carbon atoms per sulfonic acid molecule and preferably (III)at least about twelve aliphatic carbon atoms. Generally x will be aninteger of 1-3. The variables r and y have an average value of one toabout four per molecule.

The variable R in Formula V is an aliphatic or aliphatic-substitutedcycloaliphatic hydrocarbon or essentially hydrocarbon radical. Where Ris an aliphatic radical, it should contain at least about fifteen toabout eighteen carbon atoms and where R is an aliphaticsubstituted-cycloaliphatic group, the aliphatic substituents shouldcontain a total of at least about twelve carbon atoms. Examples of R arealkyl, alkenyl, and alkoxyalkyl radicals and aliphatic-substitutedcycloaliphatic radicals wherein the aliphatic substituents are alkoxy,alkoxyalkyl, carboalkoxyalkyl, etc. Generally the cycloaliphatic radicalwill be a cycloalkane nucleus or a cycloalkene nuceus such ascyclopentane, cyclohexane, cyclohexene, cyclopentene, and the like.Specific examples of R are cetyl-cyclohexyl, laurylcyclohexyl,cetyl-oxyethyl and octadecenyl radicals, and radicals derived frompetroleum, saturated and unsaturated parafiin wax, and polyolefins,including polymerized monoand diolefins containing from about 1 to 8carbon atoms per olefin monomer unit. The groups T, R, and R in FormulaeIV and V can also contain other substituents such as hydroxy, mercapto,halogen, nitro, amino, nitroso, carboxy, lower carboalkoxy, etc., aslong as the essentially hydrocarbon character of the groups is notdestroyed.

Illustrative examples of the sulfonic acids are mahogany sulfonic acids,petrolatum sulfonic acids, monoand poly- Wax-substituted naphthalenesulfonic acids, cetylchlorobenzene sulfonic acids, cetylphenol sulfonicacids, cetylphenol disulfide sulfonic acids, cetoxycapryl benzenesulfonic acids, dicetyl thianthrene sulfonic acids, di-laurylbeta-naphthol sulfonic acids, dicapryl nitronaphthylene sulfonic acids,parafiin wax sulfonic acids, unsaturated parafiin wax sulfonic acids,hydroxy-substituted parafiin wax sulfonic acids, tetraisobutylenesulfonic acids, tetraamylene sulfonic acids, chloro-substituted paraflinwax, nitrosyl-substituted paraffin wax sulfonic acids, petroleumnaphthene sulfonic acids, cetylcyclopentyl sulfonic acids, laurylcyclohexyl sulfonic acids, monoand polyWax-substituted cyclohexylsulfonic acids, and the like.

As used herein, the terminology petroleum sulfonic acids orpetrosulfonic acids is intended to cover that well-known class ofsulfonic acids derived from petroleum products according to conventionalprocesses such as disclosed in U.S. Pats. 2,480,638; 2,483,800; 2,717,-265; 2,726,261; 2,794,829; 2,832,801; 3,225,086; 3,337,- 613; 3,351,655;and the like. Sulfonic acids falling Within Formulae IV and V arediscussed in prior U.S. patents as 2,616,904; 2,616,905; 2,723,234;2,723,235; 2,723,236; 2,777,874; and the other U.S. patents referred toin each of these patents. Thus it is seen that these oil-solublesulfonic acids are well-known in the art and require no furtherdiscussion herein.

Of course, mixtures of the above-described organic acids and derivativesthereof susceptible to overbasing can be employed in the processes ofthis invention to prepare basic magnesium salts. In fact, as describedbelow, some mixtures of acids constitute preferred embodiments of theinvention.

The principal source of magnesium in the processes of the presentinvention is active magnesium oxide. Magnesium oxide is commerciallyavailable in two forms, a socalled light or active form and a relativelyinactive form known as dead burned or heavy magnesium oxide. Activeforms of magnesium oxide are available from various chemical companiesunder such names as Morton Elastomag 20, Elastomag 100, iElastomag 170;and Dow Synthetic Magncsite, Calcincd. The use of magnesium oxide inlieu of magnesium metal as is used in many of the prior art processesnot only avoids the problems associated with the storage, handling, andreactions of magnesium metal but offers a tremendous economic advantage.At current prices, based on the magnesium content, magnesium in the formof magnesium oxide costs less than one-fourth the price of magnesiummetal.

An important distinction between the present processes and the processesof the prior art is that water alone can be used as an effectivepromoter. Generally speaking, the prior art has utilized alcohols,aminoalcohols, glycols, phenols, and the like as promoters in overbasingprocesses. The amount of water to be used in the present processesdepends largely upon the amount of magnesium oxide employed. Generally,at least about one-tenth mole of water is used for each mole ofmagnesium oxide employed. Molar ratios of Water to magnesium oxide of upto about 5:1 can be used in the present process although there is atendency for the resulting product to be hazy when such large amounts ofWater are utilized. While the reason for this haziness is not completelyunderstood, it is believed that large amounts of water make possible thecrystal growth of the magnesium salts produced. Generally, the molarratio of water to magnesium oxide will be from about 0.5: 1.0 to about3.0: 1.0.

As mentioned above, when water alone is used as the promoter, there is atendency for the product to be hazy. It has been determined that if thewater is used in combination with a lower alcohol, this tendency can begreatly reduced or completely eliminated. While lower aliphaticalcohols, that is, alcohols containing up to seven aliphatic carbonatoms can be used effectively, it is preferred that the alcohol promoterhave a boiling point less than water i.e., 100 C., for reasons explainedmore fully hereinafter. Suitable alcohol promoters include methanol,ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol,n-hexanol, ethylene glycol, propylene glycol, trimethylene glycol,2-mercaptoethanol, 2-aminoethanol, 2-methoxyethanol, 2 propoxyethanol, 2butoxyethanol, and the like. The preferred alcohol promoters are thelower alkanols, particularly those containing not more than four carbonatoms such as methanol, ethanol, npropanol, isopropanol, etc. Mixturesof various alcohols are also suitable alcoholic promoters for use incombination with water. Obviously mixtures of two or more of thesepreferred lower alkanols are also useful. Methanol is the most preferredalcohol promoter although ethanol and isopropanol are also particularlyuseful alcoholic promoters for use in combination with the water. Bestresults seem to be achieved if methanol constitutes at least about 25%by weight of the total weight of any alcohol employed as a co-promoter.

Since the process is operative without the alcoholic promoter, that is,with water alone, it is apparent that there is no critical minimumamount of alcohol from the standpont of operability. Ordinarily,however, in order to achieve the best haze-eliminating or reducingcapabilities of the combination of alcohol and Water as a promotersystem, at least about 0.1 mole of alcohol should be used with each moleof water employed. When the combination of alcohol and water is used asa promoter system, the amount of water utilized remains that discussedhereinabove for water alone. Best results are achieved when thealcohol-Water molar ratio is within the range of about 0.5 :1 to about10:1. Normally, the molar ratio of alcohol to water will be about 0.8:1to about 3:1. Molar ratios of about 1:1 to about 2:1 provide anexcellent starting point from which to determine the optimum ratio ofalcohol and water for any given combina tion of acid, alcohol, andwater.

The process of the present invention is conducted in the presence of atleast one substantially inert organic liquid diluent. This diluentshould comprise at least about 10% by Weight of the total weight of thereaction mixture prior to contacting the mixture with acidic gas.Ordinarily, the diluent will not exceed by weight of the reactionmixture. Preferably, the diluent will comprise from about 30% to about70% of the reaction mass. Suitable diluents include mineral oils,Stoddard solvent, aliphatic, cycloaliphatic, and aromatic hydrocarbonsand the corresponding halogenated hydrocarbons such as chlorobenzenes,

and the other conventional organic diluents generally employed in theoverbasing procedures of the prior art. Preferably, the diluent selectedwill be oil-soluble.

A preferred diluent will comprise mineral oil and at least one otherdiluent which is soluble in mineral oil but is less viscous than themineral oil and, therefore, facilitates handling and filtering of thereaction mass. Suitable diluents for use in combination with mineral oilare those of the type mentioned above, that is, aliphatic,cycloaliphatic, and aromatic hydrocarbons and halogenated hydrocarbons.Specific examples include kerosene, xylene, toluene, ethylbenzene,n-propylbenzene, cumene, Stoddard solvent, fluorobenzene, chlorobenzene,bromobenzene, ofiuorotoluene, heptane, octane, nonane, decane,2,2,4-trimethylpentane, cyclohexane, cycloheptane, cyclooctane,ethylcyclohexane, and the like. For best results, it is desirable thatthis less viscous diluent comprise about 30% to about 50% by weight ofthe total weight of starting materials used in the process, particularlyin preparing products having metal ratios in excess of five. The lessviscous diluents facilitate filtration and for some reason, improveoil-solubility of the final basic magnesium product. That is, thetendency for solids to precipitate during long-term storage is reducedor eliminated. Furthermore, in the absence of these less viscousdiluents, there is a tendency in some instances, particularly inpreparing products of higher metal ratios (e.g., metal ratios in excessof five) for an unfilterable gel-like mass to form. While such gels canbe used as basic magnesium components in greases or as anti-rust,anti-corrosion protective coatings (usually 0.5 to mil thickness) onferrous metal surfaces exposed to air, moisture, and/or acidic vapors,they are not ordinarily suitable as fuel and lubricating oil additives.

In one aspect of this invention, it is preferred that the less viscousdiluent used in combination with mineral oil will have a boiling pointhigher than 75 C. and preferably higher than 90 C. This is in theprocesses using an alcohol-water promoter where carbonation is conductedfirst in the presence of alcohol and water and then in the presence ofwater. For best results, it has been determined that carbonation in thepresence of water alone should be at a temperature of at least about 75C. and preferably at least about 90 C. Since it is convenient to conductcarbonation at the reflux temperature, diluents having boiling points ofat least about 75 C. at standard pressure are preferred. For thisreason, xylene is a particularly preferred diluent since it forms anazeotrope with water boiling at 90-95 C. It offers the additionaladvantage of assisting in the removal of water upon completion of theprocess.

In its broadest aspect, the process of this invention involves mixingthe components of the reaction mixture, that is, the acids or othersuitable derivatives thereof as discussed above, active magnesium oxide,water, and diluent and introducing into this reaction mixture at leastone inorganic acidic material. The temperature at which the acidicmaterial is contacted with the remaining components of the reaction massis not critical. Thus, the minimum temperature is that temperature atwhich the reaction mixture remains fluid, that is, does not begin tosolidify. The maximum temperature is the decomposition temperature ofthe reaction component or product with the lowest decomposition point.Usually, the temperature will be in the range of about 25 200 C. andpreferably about 50- 0 C. The acidic material is conveniently contactedwith the components of the reaction mixture at the reflux temperature.The reflux temperature obviously depends upon that material having thelowest boiling point. Accordingly, where methanol is used as a promoterin combination with water, the reaction mixture will be contacted withthe acidic material at the reflux temperature of methanol. If water isthe only promoter and the component of the reaction mixture having thelowest boiling point, the reflux 10 temperature will be the boilingpoint of water or an azeotrope of water with, for example, xylene.

Generally, the acidic material is contacted with the components of thereaction mixture until there is no further reaction between thecomponents of the reaction mixture and the acidic material that is,until reaction between the components of the reaction mixture and theacidic material substantially ceases. This can be determined in a numberof ways conventional in the art. For example, if the acidic material isa gas which is being bubbled through the reaction mixture, then this endpoint is reached when the amount of gas being blown into the mixturesubstantially equals (that is, corresponds to about %-l00%) the amountof gas leaving the reaction mixture. This is readily determined by theuse of metered inlet and outlet valves for the gas. The end point canalso be ascertained by periodic measurement of the pH of the reactionmixture. At the point at which the basicity becomes substantiallyconstant, or the reaction mixture begins to become acidic, the end pointhas been reached. While it is preferable that the acidic material becontacted with the reaction mixture until there is no further reaction,useful basic magnesium salts can be prepared when the reaction mixtureis contacted with the acidic material for a period of time sufficientfor about 70% of the total acidic material to re act relative to theamount which would react if the reaction were permitted to proceed toits end point as described above.

Upon completion of the reaction between the acidic material and thecomponents of the reaction mixture, the solid components of the reactionproduct are usually removed by filtration, centrifugation or otherconvenient means. Thereafter, the reaction product is stripped,generally at reduced pressure, to remove alcohol, water, and, ifdesired, diluent having a boiling point less than mineral oil.Obviously, the reaction mixture can be stripped prior to removing solidsif desired.

The foregoing procedure preferably is modified in the manner explainedbelow if it is desired to prepare a basic magnesium salt having a metalratio in excess of about 5 or 6. In this modified procedure, alcoholmust be used as a co-promoter with the water. The reaction componentsare mixed together and this reaction mixture is then contacted with theacidic material in two stages. First, the components of the reactionmixture and the acidic material are contacted in the same manner asdescribed above until the reaction between the inorganic acidic materialand the reaction mixture substantially ceases. Thereafter, thetemperature of the reaction mixture is raised to remove substantiallyall free alcohol promoter. It is preferable to continue contacting theacidic material with the reaction mixture during this period of timethat the alcohol promoter is being removed although this is notessential. Any water that is removed during the removal of the alcoholis preferably replaced at this point. The reaction mixture withsubstantially all free alcohol removed is then contacted with the moreacidic material, usually until the liquid phase of the reaction massbecomes substantially clear. Thereafter, the reaction mass is generallyfiltered, etc., to remove solids and the water is removed by heating,generally at reduced pressures. Again, if desired, any low boilingdiluent can also be removed at this point. As mentioned hereinbefore,this two-stage procedure for contacting the reaction mixture with theacidic material results in products having little or no haze and whichare more easily filtered. Moreover, basic magnesium salts having metalratios in excess of about 5 have improved oil solubility when they areprepared by this two-stage process.

In some instances, the reaction mixture thickens when the alcoholpromoter is removed. In those cases, it is preferable that the reactionmixture be contacted with the acidic material for a sufiicient period oftime for the mixture to again become thinner or less viscous. The reasonfor the thinning of the reaction material with the continued contactingwith the acidic material is not understood, but this thinning effect isreadily observable in the product. Generally, contacting the acidicmaterial with the reaction product after removal of the alcohol promoterfor a period of one to six hours, usually two to four hours, producesthe desired clear, filterable product.

The foregoing modified procedure is useful in preparing basic magnesiumsalts having metal ratios of up to about 15 but generally not in excessof about 10 to 12.

When it is desired to prepare basic magnesium salts having unusuallyhigh metal ratios, that is, in excess of 15 the process should beconducted in a step-wise procedure. That is, a first basic magnesiumsalt should be prepared as described above and then this basic magnesiumsalt should be employed with additional magnesium oxide, promoter, andthe like to increase the metal ratio. In this manner, the metal ratio ofthe basic magnesium salts can be increased to about 30 or more. Usually,when the metal ratio is being increased by conducting the overbasingprocess in a series of two or more steps, the metal ratio is usuallyincreased in increments of about to 15 and preferably in increments ofabout 8 to 12. Thus, if in the first step, a basic magnesium salt havinga metal ratio of 10 is prepared and thereafter used as a startingmaterial in a second step of the procedure, sufiicient additionalmagnesium oxide will be added to provide a suflicient amount ofmagnesium to increase the metal ratio of the resulting product to aboutto about 25. Obviously, the metal ratio can be increased by smallerunits but this is inefiicient. On the other hand, trying to increase themetal ratio by larger increments increases the tendency of the productto form a haze or to gel.

In these modified versions of the process of the present invention, thatis, where the reaction mixture is contacted with the acidic material intwo stages, it is essential for optimum results that the acidic materialbe contacted with the reaction components at a temperature of at leastabout 75 C. and preferably at a temperature of at least about 90 C.after removal of the alcohol promoter. As the free alcohol must beremoved in these modified procedures, it is obvious why it is desirablethat the alcohol promoter used in combination with water have a boilingpoint less than that of water. Otherwise, it is necessary to remove thewater as well as the alcohol and then add water back to the mixture.Likewise, as explained above, the acidic material should be contactedwith the remaining components of the reaction mixtures at temperaturesof at least about 75 C. Accordingly, if any diluent of the mixture has aboiling point of less than this, it interferes with achieving thistemperature. Increased pressure in such instances would permit elevationof the temperature but is easily avoided by selecting diluents havingboiling points of at least 75 C. The maximum temperautre is limited onlyby the decomposition temperature of the reactants and product asexplained above but usually will not exceed 200 C. Temperature of 90150C. are preferred.

In a further modification of the process, it has been found useful toemploy a combination of at least one oilsoluble aliphatic carboxylicacid and one other oil-soluble acid of the type described hereinabove toprepare basic magnesium salts. Thus, an organic acid mixture comprisingat least one oil-soluble aliphatic carboxylic acid or other suitablederivative thereof as described above with at least one other organicacid susceptible to overbasing of the types described in detailhereinabove, e.g., on alkylated salicylic acid, a petrosulfonic acid, oran acid prepared from the condensation of phosphorus pentasulfide andpolyisobutylene having a molecular weight of about 1000, is usedaccording to this further modification as the organic acid" to beoverbased. Ordinarily, the aliphatic carboxylic acid per se or itsalkali or alkaline earth metal salts inclding magnesium salts will beused. This modification can be used effectively with water andalcohol-water promoter systems. Generally, the aliphatic carboxylic acidor derivative thereof is employed in an amount such that there is oneequivalent of the oil-soluble aliphatic carboxylic acid for each one totwenty, usually one to ten equivalents of the other organic acidspresent in the mixture, that is, an equivalent ratio of aliphaticcarboxylic acid to other acid of about 1:1 to about 1:20 but generally1:1 to about 1:10. The preferred ratio in the case of a combination ofaliphatic carboxylic acids and sulfonic acids is an equivalent ratio ofabout 1:2 to about 1:5. The combination of acids results in a moreefiicient utilization of the magnesium oxide although the reason is notknown.

It has also been determined that the presence of at least oneoil-soluble sulfonic acid or suitable derivative thereof susceptible tooverbasing, as described hereinbefore, is beneficial to the efiicientutilization of magnesium and the preparation of products having highermetal ratios when preparing basic magnesium salts of at least oneoil-soluble aromatic carboxylic acid or suitable derivatives thereofsusceptible to overbasing such as those illustrated by Formulae I-III.This modification is very useful in preparing basic magnesium salts ofhydroxy-substituted aromatic acids such as salicyclic acids. Thesehydroxysubstituted aromatic acids are exemplified by those includedwithin Formulae II and Ill. This combination of acids can be usedadvantageously with water as the only promoter or in an alcohol-waterpromotor system as described above. The sulfonic acid may be analiphatic, cycloaliphatic, or an aromatic sulfonic acid or mixtures oftwo or more such acids or derivatives thereof susceptible to overbasing,especially those sulfonic acids illustrated by Formulae IV-V. The amountof aromatic carboxylic acid and sulfonic acid, or their suitablederivatives, used in combination is such that the ratio of equivalentsis about 1:1 to about 20:1, preferably about 2:1 to about 15: 1.

A preferred process for overbasing a combination of hydroxy-substitutedaromatic carboxylic acids as described in the preceding paragraphcorresponds to that desired above for overbasing the combination oforganic acids and aliphaict carboxylic acids discussed hereinbefore.This preferred process comprises preparing basic magnesium salts bycarbonating a mixture comprising (a) M equivalents of at least onemember selected from oil soluble hydroxy-substituted aromatic carboxylicacids or equivalent derivatives thereof susceptible to overbasing, (b) Nequivalents of at least one member selected from oilsoluble sulfonicacids and equivalent derivatvies thereof susceptible to overbasing, (c)Q equivalents of basically reacting magnesium oxide where the ratio of M:N is about 1:1 to about 20:1 and the value of is from about 1.1 toabout 30 or more, usually not more than 20, and preferably about 2 toabout 12 ((1) water and (e) a substantially inert organic liquid mediumuntil the reaciton between the carbon dioxide and the mixturesubstantially ceases. The modifications, variations, and preferences inthe magnesium overbasing processes described herein are also applicableto the overbasing of M and N. Thus, aliphatic alcohols such as methanolor mixtures of methanol and other lower alkanols can be used ascopromoters. However, these co-promoters ordinarily may be deletedwithout adverse results (e.g., haze, gel formation) when preparing basicmagnesium salts from oilsoluble hydroxy aromatic acids or theirderivatives susceptible to overbasing. Likewise, xylene is a preferreddiluent, the metal ratio is usually increased in increments of 5 to 15,the acids per se or their alkali or alkaline earth metal salts ormixtures thereof are usually employed as starting materials and soforth. Further, the process can be conducted stepwise, that is, morewater and active magnesium oxide can be added and carbonation continuedfollowing the above procedure. This can be repeated until the desiredmetal ratio is reached. If desired, the reaction product can be filteredor subjected to other conventional purification techniques eitherbetween carbonation steps or upon completion of the last step.

While the primary purpose of this invention is to provide basicmagnesium salts, it is obvious from the foregoing that magnesium is notnecessarily the only metal present in the compositions produced. OtherGroup I and Group II metals may be present in the basic magnesium salts.Thus, if an alkali or alkaline earth metal salt other than a magnesiumsalt is employed as a starting material in the processes of thisinvention, the basic magnesium saltcontaining product may comprise theseother metals present in the starting materials. When metal salts areused as starting'materials, the salts can be either neutral or basic. Ifbasic, their metal ratios will not exceed about except, of course, wherethe metal is magnesium. For example, neutral or basic calcium or bariumpetrosulfonates can be employed alone or with neutral or basiccarboxylic acid alkali or alkaline earth metal salts as a startingmaterial for preparing basic magnesium salts. Metal salts can be mixedWith oil-soluble organic acids per se but, to the extent excess metal ispresent, it will generally neutralize the free acid and form neutralsalts in situ. Furthermore, it is also contemplated that, in addition tothe basically reacting magnesium oxide, other basically reacting Group11 metal compounds can be used in combination with the magnesium oxide.Thus, mixtures of magnesium oxide and barium oxide and/or calcium oxidecan be used to produce a basic salt containing magnesium, barium and/orcalcium. Similarly magnesium oxide can be used in combination with otherbasically reacting compounds such as calcium hydroxide, calciumcarbonate, barium hydroxide, cadmium oxide, strontium hydroxide, etc.Preferably, magnesium oxide will be employed alone as this generallyproduces the best results especially in making basic magnesium saltshaving metal ratios in excess of about 5 or 6.

Another variation contemplated as being within the scope of thisinvention is the alternate use of increments of magnesium oxide and atleast one other basically reacting metal compound. For example, one ormore increments of magnesium oxide can be used and the reaction mixturecarbonated or contacted with other acidic materials as described aboveand then one or more increments of calcium hydroxide, calcium oxide,barium hydroxide, etc., can be added and the resulting mixture contactedwith an acidic material. This stepwise and alternating use of differentmetals can be repeated until the desired metal ratio is achieved.

If other metals are present in the basic magnesium compositions producedaccording to the process of this invention, the amount of such othermetals will be such as not to account for more than about 40% of thetotal metal ratio and, preferably, not more than The presence of theseadditional metals does not affect the utility of the basic magnesiumsalts in any of the uses described herein. It is often desirable to usethe calcium and barium salts of the organic acids as starting materialsin preparing the basic magnesium salts of this invention.

It is to be understood that the reactants employed in the processes ofthis invention can be brought together in any desired manner. Thus,magnesium oxide and water can be mixed and added to a mixture of theremaining starting materials. Or a mixture of the inert organic diluentand alcohol can be prepared and added to a mixture of acid, water, andmagnesium oxide. Various other orders of addition and mixing are alsopossible. Moreover, the various reactants, diluents, and promoters neednot be mixed in toto at one time prior to contacting the mixture withthe acidic material but one or all may be introduced 14 continuouslyover a period of time or in portions at regular or irregular intervalsbefore or during the reaction with the acid material so long as theoverall parameters of the processes as defined above are maintained.

The processes of the present invention are illustrated by the followingexamples representing preferred embodiments thereof. The productsproduced represent specific examples of the novel, oil-soluble basicmagnesium salts of this invention.

EXAMPLE 1 A reaction mixture comprising 906 grams (1.5 equivalents) ofan oil solution of alkylphenylsulfonic acid having (average molecularweight450), 564 grams of mineral oil, '600 grams of toluene, 95.7 gramsof magnesium oxide (4.4 equivalents), and grams of water are carbonatedat a temperature of about 7885 C. for about seven hours at a rate ofabout three cubic feet of carbon dioxide per hour during which time thereaction mixture is constantly agitated. The carbonation is stopped andthe reaction product stripped by heating to 165 C. at a pressure of 20mm. (Hg.). The stripped product is filtered. The filtrate is anoil-solution of the desired basic magnesium sulfonate having a metalratio of about 3.

EXAMPLE 2 Following the general procedure of Example 1, a reactionmixture comprising 604 grams (1 equivalent) of an oil-solution of analkylated benzenesulfonic acid (average molecular weight-450), 584 gramsof mineral oil, grams of magnesium oxide, 97 grams of water, and 500grams of toluene are carbonated at 85-90 C. (reflux) for about fivehours at a rate of about 3 cubic feet of carbon dioxide per hour. Thereaction mixture is dried by blowing with nitrogen for about four hourswhile raising the temperature to about 165 C. Thereafter, the reactionproduct is stripped to 165 C. at 50 mm. (Hg) and filtered. Thefiltration is an oil-solution of the desired basic magnesium saltcharacterized by a metal ratio of about 5 EXAMPLE 3 A reaction mixturecomprising 302 grams (0.5 equiv alent) of an oil-solution of analkylphenylsulfonic acid (average molecular weight450), 139 grams (0.5equivalent) of a mixture of oil-soluble fatty acids (tall oil acids soldby Hercules under the name Pamak-4), 196 grams (9 equivalents) ofmagnesium oxide, 735 grams of mineral oil, 440 grams of toluene, and 163grams of water is carbonated at a temperature of about 8590 C. (reflux)ata rate of about 1.5 cubic feet of carbon dioxide per hour for aboutten hours with stirring. The carbonated reaction product is then blownwith nitrogen while heating to about C. to remove water and toluene andfinally stripped at reduced pressure at 160 C. The dried product isfiltered. The basic magnesium salt is characterized by a metal ratio ofabout 5.4.

EXAMPLE 4 The general procedure of Example 3 is repeated utilizing 0.75equivalent of the sulfonic acid, 0.25 equivalent of the tall oil acidmixture, and 9 equivalents of magnesium oxide, a basic magnesium salt isprepared having a metal ratio of about 8.6.

EXAMPLE 5 A reaction mixture comprising 348 grams (0.5 equivalent) of anoil solution of an alkylphenylsulfonic acid (average molecularweight-500), 240 grams of mineral oil, 600 grams of xylene, 108.5 grams(5 equivalents) of magnesium oxide, 117 grams of methanol, and 75 gramsof water is carbonated at 65 70 C. (reflux) at a rate of about 1.5 cubicfeet per hour for about 1.5 hours at which time the rate of carbondioxide uptake was less than 0.2 cubic foot per hour. Carbonation iscontinued at this rate while the temperature is raised to 95 C. toremove the methanol. After removal of the methanol, 75 grams of waterare added to the mixture and carbonation is continued at about one cubicfoot per hour at the reflux temperature (about 90 C.) until the carbondioxide uptake rate was less than 0.1 cubic foot per hour. This point isreached in about 3.5 hours. The material is then dried by heating to 140C. with continued carbonation and filtered. The filtrate is anoil-solution of the desired basic magnesium salt which is characterizedby a metal ratio of about 8.6.

EXAMPLE 6 (A) A reaction mixture comprising 1044 grams (about 1.5equivalents) of an oil solution of an alkylphenyl sulfonic acid (averagemolecular weight-500), 1200 grams of mineral oil, 2400 grams of xylene,138 grams (about 0.5 equivalent) of the tall oil acid mixture describedabove, 434 grams (20 equivalents) of magnesium oxide, 600 grams ofmethanol, and 300 grams of water is carbonated at a rate of 6 cubic feetof carbon dioxide per hour at 65 70 C. (methanol reflux). The carbondioxide introduction rate was decreased as the carbon dioxide uptakediminished. After 2.5 hours of carbonation, the methanol is removed byraising the temperature of the mixture to about 95 C. with continuedcarbon dioxide blowing at a rate of about two cubic feet per hour forone hour. Then 300 grams of water is added to the reaction mixture andcarbonation was continued at about 90 C. (reflux) for about four hours.The material becomes hazy with the addition of the water but clarifiesafter 2-3 hours of continued carbonation. The carbonated product is thenstripped to 160 C. at 20 mm. (Hg) pressure and filtered. The filtrate isan oil solution of the desired basic magnesium salt, the salt beingcharacterized by a metal ratio of about 10.

(B) Following the general procedure of (A) but adjusting the weightratio of methanol to water in the initial reaction mixture to 4:3 inlieu of the 2:1 ratio of (A), another oil-solution of a basic magnesiumsalt is produced. This methanol-water ratio gives improved carbonationat the methanol reflux stage of carbonation and prevents thickeneing ofthe mixture during the 90 C. carbonation stage.

EXAMPLE 7 A reaction mixture comprising 135 parts mineral oil (all partsare parts by weight unless otherwise indicated), 330 parts xylene, 200parts (0.235 equivalent) of a mineral oil solution of analkylphenylsulfonic acid (average molecular weight 425), 19 parts (0.068equivalent) of the above-described mixture of tall oil acids, 60 parts(about 2.75 equivalents) of magnesium oxide, 83 parts methanol, and 62parts water are carbonated at a rate of parts of carbon dioxide per hourfor about two hours at the methanol reflux temperature. The carbondioxide inlet rate is then reduced to about 7 parts per hour and themethanol is removed by raising the temperature to about 98 C. over athree-hour period. Then 47 parts of water are added and carbonation iscontinued for an additional 3.5 hours at a temperature of about 95 C.The carbonated mixture is then stripped by heating to a temperature ofl40145 C. over a 2.5-hour period. This results in an oil solution of abasic magnesium salt characterized by a metal ratio of about 10.

Then, the carbonated mixture is cooled to about 60- 65 C. and 208 partsxylene, 60 parts magnesium oxide, 83 parts methanol and 62 parts waterare added thereto. Carbonation is resumed at a rate of 15 parts per hourfor two hours at the methanol reflux temperature. The carbon dioxideaddition rate is reduced to 7 parts per hour and the methanol is removedby raising the temperature to about 95 C. over a three-hour period. Anadditional 41.5 parts of water are added and carbonation is continued at7 parts per hour at a temperature of about 90-95 C. for 3.5 hours. Thecarbonated mass is then heated to about 150160 C. over a 3.5-hour periodand then further stripped by reducing the pres- 1 6 sure to 20 mm. (Hg)at this temperature. The carbonated reaction product is then filtered.The filtrate is an oilsolution of the desired basic magnesium saltcharacterized by a metal ratio of 20.

EXAMPLE 8 A reaction mixture comprising 350 grams (0.5 equivalent) of anoil-solution of an alkylphenyl sulfonic acid (average molecularweight450), grams (about 4 equivalents) of magnesium oxide, 122 grams ofethanolamine, 680 grams of xylene, 100 grams of water, and 250 grams ofmineral oil are carbonated at a rate of 3 cubic feet of carbon dioxideper hour at a temperature of -100 C. for one hour. The carbonation isstopped, 25 grams of water added and the resulting carbonated mixture isrefluxed for about 1.5 hours, stripped to 170 at 25 mm. (Hg), andfiltered. The filtrate is an oil solution of the desired basic magnesiumsalt. The salt is characterized by a metal ratio of about 6.8.

EXAMPLE 9 A reaction mixture comprising 2900 grams (3 equivalents) of anoil solution of the magnesium salt of polyisobutylene (average molecularweight480)-substituted salicyclic acids, 624 grams of mineral oil, 277grams (1 equivalent) of the commercial mixture of tall oil acidsdescribed hereinabove, 1800 grams of xylene, 195 grams (9 equivalents)of magnesium oxide, and 480 grams of water are carbonated at the refluxtemperature (about C.) for one hour. The carbonated mixture is thenstripped by first heating to 160 C. with nitrogen blowing (3 cubic feetper hour) and thereafter heating to 165 C. at a pressure of 30 mm. (Hg).This stripped carbonated product is filtered, the filtrate being an oilsolution of the desired basic magnesium salt. The salt is characterizedby a metal ratio of 2.7.

EXAMPLE 10 (a) To a thoroughly agitated mixture comprising 232 parts ofalkylated benzene sulfonic acid (0.33 equivalent), 160 parts mineral oildiluent, 400 parts xylene, and 72 parts magnesium oxide (3.33equivalents) heated to about 30 C., there is added 50 parts water andthe temperature is increased to about 90-95 C. This mixture is blownwith H S gas until the reaction with H 5 substantially ceases as shownby the fact that the quantity of H S evolving from the mixture issubstantially equal to that being introduced into the mixture. Then, anadditional 20 parts water is added and the H 8 blown mixture is blownwith carbon dioxide until the CO uptake substantially ceases whilemaintaining a temperature of 85- 95 C. Water is removed as an azeotropewith xylene by heating the carbonated mixture to C. with continued COblowing to assist in the water removal. The dried mixture is thenfiltered and the filtrate stripped to a temperature of C. and a pressureof 40 mm. (Hg). The filtrate is a 30% oil solution of the desired basicmagnesium salt having a metal ratio of about 6.4. The filtrate ischaracterized by a sulfur content of 2.93%, a sulfate ash content of24.4% and a C0 content of 4.9%.

(b) Hydrogen sulfide gas is introduced via a submerged inlet line into areaction mixture comprising 232 parts (0.33 equivalent) of the sulfonicacid of (a), 160 parts mineral oil diluent, 400 parts xylene, 72 parts(3.33 equivalents) magnesium oxide, 80 parts methanol, and 50 partswater while maintaining a temperature of 35 40 C. until the H S uptakesubstantially ceases. The temperature is then raised to 60 C. while H Sblowing is maintained. Upon reaching 60 C., H S blowing is discontinuedand CO blowing is initiated and continued until the amount of COintroduced substantially equals that existing the reaction mass. Then,the methanol is distilled while CO blowing is continued. Fifty parts ofwater are added and the resulting mixture is carbonated at the refluxtemperature (about 90 C.) for about four hours at which time thereaction mixture is clear and thin, (i.e., has a lowviscosity). Water isremoved as an azeotrope with the xylene. The resulting dried mixture isthen stripped to 160 C. at 20 mm. pressure, (Hg) and filtered; Thefiltrate is an oil solution of the desired basic magnesium salt having ametal ratio of about 8.3. The The filtrate is further characterized by asulfate ash content of 31.6%, a C content of 6.9%, and a sufur contentof 2.25%.

If the process is terminated at the conclusion of the H S blowing stepand that product is stripped, filtered, etc., a non-carbonated basicmagnesium salt-containing filtrate is produced.

EXAMPLE 11 A thoroughly agitated mixture comprising 232 parts (0.33equivalent) of the alkylated benzene sulfonic acid of Example 5, 410parts mineral oil diluent, 100 parts xylene, 72 parts (3.33 equivalents)magnesium oxide, 50 parts heptylphenol, 80 parts methanol, and 50 partswater is carbonated by blowing CO through the mixture while maintainingthe methanol reflux temperature until the CO uptake substantiallyceases. While carbonation is continued, the temperature is increased to95 C. to distill off the methanol. An additional 50 parts water is addedand the resulting mixture is carbonated an additional three and one-halfhours at the reflux temperature (about 90 C.). The resulting mixture isfiltered and the filtrate stripped to 165 C. at 40 mm. (Hg) pressure toproduce an oil solution of the desired basic magnesium salt which ischaracterized by a metal ratio of about 8.5.

This example demonstrates the use of an auxiliary phenolic promoter in aprocess of this invention. It is contemplated that one or more otherknown phenolic promoters can be used in conjunction with thewateralco'hol co-promoter system of the magnesium overbasing processesdescribed herein without departing from the scope of the presentinvention.

When auxiliary phenolic promoters are used, the amount of phenolicpromoter ordinarily should be such that the number of equivalents ofphenolic promoter does not exceed the number of equivalents of alcoholcopromoter and preferably does not exceed about half the number ofequivalents of alcohol co-promoter. Phenolic promoters have oneequivalent per phenolic OH group and alcohols have one equivalent peralcoholic OH group. Thus monohydric alcohols such as methanol, ethanol,etc., have one equivalent per mole; dihydric alcohols have twoequivalents per mole, etc. Likewise, alkylated phenols and alkylatednaphthols have one equivalent per mole. Thus, monohydric phenols such asheptylphenols, octylphenols, nonylphenols, etc., have one equivalent permole. Other suitable phenolic promoters include cetylphenols, octylcatechols, hexylphenols, triisobutyl naphthols, and the like.

EXAMPLE 12 (a) A mixture comprising 174 parts (0.25 equivalent) of analkylated benzene sulfonic acid, 23 parts (0.083

equivalent) Pamak4 fatty acid mixture, 199 parts mineral oil diluent,250 parts Stoddard solvent, 72 parts (3.33 equivalents) magnesium oxide,75 .parts methanol and 72 parts water is carbonated at the refluxtemperature (70-75 C.) until the CO uptake substantially ceases. Thenthe methanol is removed by distillation while CO blowing is continued.After removal of the methanol, carbonation is continued at the refluxtemperature of the remaining mixture for thirty minutes. Then thecarbonated reaction mixture is stripped to 165 C. at 20 mm. (Hg)pressure and filtered. The filtrate is an oil solution of the desiredbasic magnesium salt having a metal ratio of about 8.5. The filtrate hasa sulfate ash content of 32.5%.

(b) The general procedure of (a) is repeated but the amount of Stoddardsolvent is increased to 400 parts and the amount of methanol isincreased to 100 parts. The

amount of Water initially employed is reduced to 50 parts.

After removal of the methanol, 50 additional parts of Water are addedand carbonation is continued for 3.5 hours. The filtrate ischaracterized by a sulfate ash content of about 36.3% and contains thedesired basic magnesium salt having a metal ratio of about 9.5.

(c) The procedure of (a) is repeated substituting sulfur dioxide forcarbon dioxide to produce a non-carbonated basic magnesium salt.

EXAMPLE 13 Following the procedure of Example 12(b), a mixturecontaining 218 parts (0.25 equivalent) of alkylated benzene sulfonicacid, 25 parts (0.083 equivalent) of isostearic acid, and 72 parts (3.33equivalents) of magnesium oxide is carbonated to produce a filtratehaving a sulfate ash content of 36.6% and containing a basic magnesiumsalt having a metal ratio of about 9.6.

EXAMPLE 14 (a) A mixture comprising 1313 parts (1.5 equivalents) of analkylated benzene sulfonic acid having an equivalent weight of 875, 138parts (0.5 equivalent) of the commercial mixture of carboxylic acidsdescribed in Example 3, 432 parts (20 equivalents) magnesium oxide, 921parts mineral oil diluent, 2400 parts xylene, 600 parts methanol, and300 parts water is carbonated at about 70 C. until CO uptakesubstantially ceases. While maintaining carbon dioxide blowing, themethanol is removed by distillation and 400 parts water are added.Carbonation is continued while maintaining a temperature of about C.until the CO uptake again substantially ceases. The resulting carbonatedmass is then stripped to 165 C. at 20 mm.(Hg) pressure and filtered. Thefiltrate is an oil solution of the desired basic magnesium salt having ametal ratio of 10. The filtrate is further characterized by a C0 contentof about 9.1% and a sulfate ash content of about 38.6%.

(b) A mixture comprising 422 parts of the filtrate of (a), 40 partsmineral oil, 400 parts xylene, 37 parts magnesium oxide, parts methanol,and 50 parts water is carbonated at the reflux temperature (65 70 C.)until the CO uptake substantially ceases. While continuing carbonationthe methanol is removed by distillation and then 50 parts water areadded. The temperature is increased to about 90 C. and the CO blowing ismaintained until the CO uptake again substantially ceases. Thecarbonated material is stripped to C. at 40 mm. (Hg) pressure andfiltered. The filtrate is an oil solution of the desired basic magnesiumsalt having a metal ratio of about 16.3. The filtrate is furthercharacterized by a sulfate ash content of about 52.3% and a C0 contentof about 12.4%.

(c) Th procedure of (b) is repeated using 522 parts of the filtrate of(a) and 36 parts of magnesium oxide. The filtrate is characterized by asulfate ash content of about 47.7% and a C0 content of about 11.6%. Thebasic magnesium salt has a metal ratio of about 15.

(d) The procedure of (c) is repeated using 72 parts magnesium oxide. Thefiltrate is characterized by a sulfate ash content of about 58.5% and aC0 Content of about 14.2%. The basic magnesium salt has a metal ratio of20.

(e) The procedure of (c) is repeated using 88 parts magnesium oxide. Thefiltrate is an oil solution of the desired basic magnesium salt having ametal ratio of about 22.

(f) The procedure (c) is repeated using 570 parts of the filtrate of (c)in lieu of the filtrate of (a) and 100 parts mineral oil diluent in lieuof 30. The resulting filtrate is a mineral oil solution of the desiredbasic magnesium salt having a metal ratio of about 27.

EXAMPLE 15 (a) A mixture comprising 801 parts (3 equivalents) of thecarboxylic acid mixture described in Example 3, 198 parts (9equivalents) of magnesium oxide, 900 parts of xylene, 900 parts mineraloil diluent, and 360 parts water is carbonated at about 95 C. until theCO uptake substantially ceases. While maintaining the CO blowing, thereaction mixture is stripped to 160 C. at mm. (Hg) pressure andfiltered. The filtrate is an oil solution of the desired basic magnesiumcarboxylates (metal ratioabout 2.4) and is characterized by a sulfateash content of about 21.5%.

(b) The general procedure of (a) is repeated but 300 parts of methanolare incorporated into the original mixture and the amount of waterpresent is reduced to 225 parts. The carbonation is conducted in twostages, the first at 55-65 C. and the second, after the methanol isdistilled off and 75 parts water are added, about 9095 C. Afterstripping and filtration, the filtrate is characterized by a sulfate ashcontent of about 22.7% and the basic magnesium salt is characterized bya metal ratio of about 2.5.

(c) The procedure of (b) is repeated using a 300 parts of an equimolarmixture of methanol and isopropanol with substantially the same results.

EXAMPLE 16 (a) A magnesium sulfonate is prepared by heating a mixture of4122 parts (6 equivalents) of the sodium salt of an oil-soluble alkylbenzene sulfonic, 1960 parts mineral oil diluent, 300 parts magnesiumchloride (MgCl and 600 parts water at 80110 C. for about three hours.The reaction mixture is then stripped while blowing with nitrogen andfiltered.

(b) A mixture comprising 1530 parts 1.5 equivalents of acid moiety) ofthe filtrate of (a), 138 parts (0.5 equivalent) of the commercialmixture of carboxylic acids described in Example 3, 390 parts (18equivalents) of magnesium oxide, 708 parts mineral oil diluent, 2400parts xylene, 600 parts water and 600 parts methanol is carbonated atabout 7075 C. until the CO uptake substantially ceases. The methanol isthen distilled off and 300 parts additional water added withoutinterrupting the CO blowing. When the CO uptake again substantiallyceases, the carbonated mixture is stripped to 165 C. at 20 mm. (Hg)pressure and filtered. The filtrate is characterized by a sulfate ashcontent of 37.1% and contains the desired basic magnesium salt (metalratioabout 9.7).

(c) To a mixture of 1380 parts (2 equivalents) of the sodium salt of analkylated benzene sulfonic acid, 138 parts of the carboxylic acidmixture described in Example 3, and 2400 parts xylene, there is added100 parts (2.1 equivalents) of MgCl dispersed in 600 parts methanol. Themixture is heated at about 50 C. for one hour. Subsequently, 390 parts(18 equivalents) of magnesium oxide and 544 parts water are added andcarbonation is commenced while maintaining a temperature of about 70 C.After the CO uptake substantially ceases, the methanol is distilled ohand 300 parts water are added, during which carbon dioxide blowing iscontinued while maintaining a temperature of about 90 C. When the COuptake again substantially ceases (i.e., CO introduced is one standardcubic foot per hour and that evolving from the reaction mass is about0.9 standard cubic feet), the reaction mixture is stripped to 165 C. at20 mm. (Hg) pressure and filtered. The filtrate has a sulfate ashcontent of 26.5% and the basic magnesium salt is characterized by ametal ratio of about 5.5.

(d) The procedure of (c) is repeated substituted 860 parts ethanol forthe 600 parts methanol. The first carbonation is conducted at about 7880C.

EXAMPLE 17 A mixture comprising 1330 parts of a 58% mineral oil solutionof a normal barium petrosulfonate containing 0.25 equivalent ofpetrosulfonic acid (in the form of the barium salt), 23 parts (0.08equivalent) of the carboxylic acid mixture of Example 3, 7.5 parts (0.08equivalent) of barium hydroxide monohydrate, 95 parts mineral oildiluent and 400 parts xylene is heated at about 50 C. Then 100 partsmethanol is added followed by 72 parts (3.3 equivalents) magnesium oxideand finally, 60 parts water. The resulting mixture is carbonated at 6065C. until the CO uptake substantially ceases. The carbonated mass is thenstripped to 165 C., blown with nitrogen at that temperature for onehour, and filtered. The filtrate is a 48.8% oil solution of the desiredbasic magnesium salt and is characterized by a sulfate ash content of35.8%, and a barium content of about 3.9%. The metal ratio of the saltis 9.35. The theoretical ratio based on the total equivalents of bariumand magnesium employed is 11.

EXAMPLE 18 A mixture comprising 448 parts (0.4 equivalent) of aphosphorous-containing acid having a sulfur content of 2.75% prepared byhydrolyzing the reaction product of 1000 parts of polyisobutylene(having an average molecular weight of 1000) and parts of P 8 reacted at260 C. (according to conventional procedures for preparing such acids),30 parts (0.04 equivalent) of an alkylated benzene sulfonic acid, 52parts (2.4 equivalents) of magnesium oxide (Dow calcined magnesite), 80parts mineral oil diluent, 500 parts xylene, 100 parts methanol, and 100parts water is carbonated until the CO uptake substantially ceases. Thecarbonated material is stripped to 160 C. while continuing CO blowingand then filtered. The filtrate is an oil solution of the desired basicmagnesium salt. The salt is characterized by a metal ratio of about 2.4.

EXAMPLE 19 (a) A mixture comprising 1615 parts (2.33 equivalents) ofalkylated benzene sulfonic acids, 200 parts (0.77 equivalent) of Century1210 carboxylic acids, 585 parts (27 equivalents) of magnesium oxide(Dow calcined magnesite), 1356 parts mineral oil diluent, 3200 partsxylene, 800 parts methanol, and 400 parts water is carbonated at themethanol reflux temperature until the CO uptake substantially ceases.The carbonated material is stripped to C. to remove methanol and 400parts water are added. The resulting mixture is then carbonated at aboutC. until the CO uptake again substantially ceases. Then the mixture isstripped to 180 C. at 38 mm. (Hg) pressure and filtered. The filtrate ischaracterized by a sulfate ash content of about 38.8%. The basicmagnesium salt is characterized by a metal ratio of about 8.4.

(b) The procedure of (a) is repeated using 0.77 equivalent of Hydrex 440carboxylic acids in lieu of the Century 1210 acids. The basic magnesiumsalt has a metal ratio of about 8.7 and the filtrate is characterized bya sulfate ash content of about 38.4%.

Century 1210 and Hydrex 440 are the names of carboxylic acid mixturesavailable from the Harchem Division of Pennwalt Corporation. Themanufacturers analysis (approximate percent by weight composition) ofeach product is as follows: Century 1210: 1.5% myristic acid, 0.5%pentadecylic acid, 52% palmitic acid, 1.5% margaric acid, 37.5% stearicacid, and 7.0% oleic acid. Hydrex 440: 4% myristic acid, 0.5 entadecylicacid, 29% palmitic acid, 1.5% margaric acid, 56.5% stearic acid, 1%arachidic acid, 0.5 palmitoleic acid, and 7.0% oleic acid.

EXAMPLE 20 (a) To a mixture comprising 776 parts of a 60% oil solutionof neutral calcium petrosulfonate containing 0.67 equivalent ofpetrosulfonic acid as the calcium salt, 46 parts (0.17 equivalent) ofthe carboxylic acid mixture of Example 3, 800 parts xylene, and partsmethanol, there is added 130 parts magnesium oxide followed by 250 partswater. The resulting mixture is carbonated at 6062 C. until the COuptake substantially ceases. Then the carbonated material is stripped toC. at 25 mm. (Hg) pressure and filtered. The filtrate is characterizedby a sulfate ash content of 36.1% and contains 21 the desiredcalcium-containing basic magnesium salt (metal ratio-74).

(b) The general procedure of (a) is repeated but 6 parts (0.16equivalent) of calcium hydroxide is added to the initial mixture and themixture is heated to 50 C. before adding the magnesium oxide and waterand carbonating. The calcium-containing basic magnesium salt has a metalratio of 7.4 and the filtrate is characterized by a sulfate ash contentof about 36.4%.

EXAMPLE 21 (a) Neutral magnesium salts of polyisobutenyl (averagemolecular weight3 00)substituted salicyclic acids are prepared by adouble decomposition reaction involving mixing 7850 parts of a 43%mineral oil solution of the corresponding potassium salt, containingabout 7.5 equivalents of the acid in the form of the potassium salt,with 500 parts toluene and 770' parts (7.6 equivalents) of MgCl -6H O in500 parts water and heating at reflux for about two hours. The resultingmixture is stripped to 160 C. While blowing with nitrogen and filtered.

(b) A mixture comprising 2900 parts of the filtrate of (a) containing 3equivalents of acid as the neutral magnesium salt, 300 parts (1equivalent) isostearic acid, 195 parts (9 equivalents magnesium oxide),600 parts mineral oil, 1800 parts xylene, and 480 parts water iscarbonated at the reflux temperature until the CO uptake substantiallyceases. The material is stripped to 160 C. with nitrogen blowing to 2 8mm. (Hg) pressure and filtered. The filtrate is a 45.3% oil solution ofthe desired basic magnesium salt which has a metal ratio of about 2.8.The sulfate ash content of the filtrate is 16.2%.

(c) The procedure of (b) is repeated substituting 1 equivalent ofCentury 1210 acid for the isostearic acid. The filtrate has a sulfateash content of 16.3%.

(d) The procedure of (b) is repeated substituting 1 equivalent of Hydrex440 for the isostearic acid. The filtrate has a sulfate ash content of16.5%.

EXAMPLE 22 A mixture comprising 512 parts of the filtrate of Example21(a) containing 0.5 equivalent of polyisobutenylsubstituted salicylicacid as the neutral magnesium salt, 31 parts of a mineral oil solutionof alkylated benzene sulfonic acids containing 0.037 equivalents ofsulfonic acid, 22 parts (1 equivalent) of magnesium oxide, 250 partsxylene, and 60 parts water is carbonated, stripped, and filteredaccording to the general procedure of Example (b). The filtrate is a 38%oil solution of the desired basic magnesium salt which has a metal ratioof about 2.7. The filtrate is characterized by a sulfate ash content ofabout 14.7%.

EXAMPLE 23 (a) A mixture comprising 277 parts (1 equivalent) of thecarboxylic acid mixture of Example 3, 179 parts (8.2 equivalents)magnesium oxide, 179 parts water, 179 parts methanol, 615 parts xylene,and 393 parts mineral oil diluent is carbonated at 60-70 C. until the COuptake substantially ceases. The methanol distilled off by heating to 95C. with continued CO blowing and 175 parts water are added. Carbondioxide blowing is continued at 90-95 C. until the CO uptake againsubstantially ceases. While maintaining the CO blowing the carbonatedmass is stripped to 160 C. and subsequently filtered. The filtrate is a40% oil solution of the desired basic magnesium salts (metal ratio of3.8) and is characterized by a sulfate ash content of 23.1%.

(b) The procedure of (a) is repeated with the following modifications.The amount of xylene is increased to 816 parts and the amount ofmethanol is increased to 250 parts while the amount of water pressure inthe initial mixture is 125 parts. After removal of the methanol, 50parts water and 100 parts butyl alcohol are added and carbonation iscontinued at 80-84 C. until the CO 22 uptake again substantially ceases.After stripping and filtration, a 40% oil solution of the desired basicmagnesium salt (metal ratio-3.5) is obtained and is characterized by asulfate ash content of 21.5%.

This example illustrates preparation of the basic magnesium salt usingtwo different alcohols as co-promoters with Water. The butyl alcoholpermits a higher carbonation temperature. A hexyl, pentyl, heptylalcohol etc., could also have been used. Furthermore the butyl alcoholand methanol could have been employed as a mixture of alcoholicco-promoters initially and the methanol selectively distilled off withthe same results. Such variations as these are contemplated as beingwithin the scope of the present inventions.

EXAMPLE 24 (a) To a mixture comprising 190 parts (0.25 equivalent) ofalkylated benzene sulfonic acid, 400 parts xylene, 157 parts mineral oildiluent, 23 parts (0.083 equivalent) of the carboxylic acid mixturedescribed in Example 3, and 72 parts (3.33 equivalents) magnesium oxideheated to about 50 C. there is added parts methanol and 75 parts water.The temperature is maintained at 5060 C. While carbonating via asubmerged CO inlet line until the CO uptake substantially ceases. Themethanol is distilled ofii with continued CO blowing and 50 parts wateradded. The CO blowing is continued at a temperature of about 90 C. untilthe CO uptake again substantially ceases. The carbonated mass is thenstripped to C. at 25 mm. (Hg) pressure. To the stripped mixture there isadded 26 parts polyisobutenyl (average molecular weight1000)-substitutedsuccinic anhydride. The resulting mixture is heated at about 160 C. withnitrogen blowing for about one-half hour and filtered. The filtrate ischaracterized by a sulfate ash content of about 37.8% and the basicmagnesium salt thus produced has a metal ratio of about 9.9-. Thepurpose of the succinic anhydride is to improve the solubility of thebasic magnesium salts, particularly on long-standing in storage, and toimprove their water-tolerance capabilities, e.g., their ability not toform emulsions or precipitate in the presence of contaminating amountsof water encountered in storage and use.

(b) The procedure of (a) is repeated using sulfur dioxide gas (SO inlieu of carbon dioxide to produce the desired non-carbonated basicmagnesium salt.

In lieu of the polyisobutenyl-substituted succinic acid anhydride otheroil-soluble high-molecular weight monoor polycarboxylic acids, theiranhydrides containing about 30-700 aliphatic carbon atoms, and/oracylated nitrogen compounds and esters derived therefrom can be used toimprove the lubricating oil and fuel solubility characteristics of thebasic magnesium salts of this invention. Preferably, such material usedto improve the solubility will contain at least about fifty aliphaticcarbon atoms. The solubility improvers constitute an art-recognizedclass of compounds used extensively as detergent-dispersants inlubricants and fuels and/or as intermediates in their preparation. Forexample, polyolefin-substituted acrylic acids, methacrylic acids, andsuccinic acids and their equivalent acylating derivatives have beenreacted with various amine compounds such as alkylene polyamines,aminoalkyl piperazines, etc., to produce amides and imides usedextensively as lubricating oil additives. Similarly, the acylatingagents can be reacted with polyhydric alcohols, polyoxyalkylene glycols,etc. to produce esters useful as fuel and lubricant additives. Thesedetergent-dispersants and/ or their intermediates are disclosed in suchUS. patents as 3,346,354; 3,341,542; 3,272,746; 3,219,666; 3,216,936;3,200,107; 3,172,892; 3,288,714; 3,381,022; and 3,331,776, all of whichare incorporated herein for the sake of brevity. While the foregoingexamples demonstrate the addition of the anhydride after carbonation andstripping are complete, such solubility improvers can be employed in anystep in the procedure from the initial reaction mixture to additionafter filtration. In fact, if a tendency to haziness or gelation isencountered, the solubility improver can be employed advantageously atthat point (or just prior to that point) in the procedure where thehaziness or gelation arises. Ordinarily the solubility improver, ifemployed, will be used in amounts of from about 0.1% to about by weightbased on the total weight of the composition. Amounts of about 1%-10%are particularly useful. Obviously, since the solubility improvers areuseful lubricant and fuel additives, their presence in the final productis not detrimental to the utility of the basic magnesium salts.

EXAMPLE (a) A mixture comprising 394 parts (0.5 equivalent) of a 16% oilsolution of alkylated benzene sulfonic acid, 46 parts (0.16 equivalent)of the carboxylic acid mixture of Example 3, 614 parts mineral oildiluent, 500 parts xylene, and 100 parts water is heated to 50 C., 144parts (6.65 equivalents) magnesium oxide is added, and the resultingmixture is heated at 5060 C. for about one-half hour. Then 133 partsboric acid (H BO is added and the reaction mixture is heated at refiux(about 97 C.) for two hours. The temperature is elevated to 160 C.during which time water and xylene distill ofi and the mass is heated atthat temperature for six hours. The re action product is then strippedto 170 C. at a pressure of mm. (Hg) and filtered twice to produce 200parts of filtrate which is an oil-solution of the desired basicmagnesium salt. The salt is characterized by a metal ratio of 6.5 (basedon the sulfonic acid) and the filtrate has a sulfate ash content ofabout 20.8% and a boron content of about 1.09%.

(b) To a mixture containing 394 parts (0.5 equivalent) of a 16% oilsolution of alkylated benzene sulfonic acid, 46 parts (0.16 equivalent)of the carboxylic acid mixture of Example 3, 314 parts mineral oildiluent, 600 parts xylene, and 100 parts water heated to about 50 C.there is added 144 parts (6.65 equivalents) of magnesium oxide. Thismixture is heated at reflux for one hour and 248 parts boric acid areadded. The boric acid containing mixture is heated at reflux for 3.5hours, the last 2.5 hours being accompanied by carbon dioxide blowinguntil the CO uptake substantially ceases. Water is then removed bydistillation and the resulting mixture filtered. The filtrate isstripped to 155 C. to 25 mm. (Hg) pressure. The filtrate is an oilsolution of the desired basic magnesium salt and is characterized by aboron content of about 2.6%, a C0 content of 0.59%, and a sulfate ashcontent of 31.3%. The metal ratio of the salt (based on the sulfonicacid) is about 8.2.

EXAMPLE 26 To a mixture comprising 448 parts (0.4 equivalent) of thephosphorus acid described in Example 18, 30 parts (0.04 equivalent) ofthe alkylated benzene sulfonic acid oil solution of Example 25 (a), 500parts xylene, and 80 parts mineral oil diluent heated to about 60 C.,there is added 100 parts methanol, 24 parts (1.1 equivalent) ofmagnesium oxide, and 100 parts water. This mixture is carbonated at 6070C. until the CO uptake substantially ceases. The reaction mixture isstripped first to 120 C. with continued carbon dioxide blowing and thento 160 C. at 50 mm. (Hg) pressure with nitrogen blowing. Uponfiltration, 555 parts of filtrate are recovered, the filtrate being anoil solution of the desired basic magnesium salt. The filtrate has amagnesium content of about 1.78% and the basic magnesium salt has ametal ratio of about 2.

From the foregoing description of the invention and the illustrativeexamples, it is apparent that the total amount of magnesium oxideemployed need not be incorporated into the basic magnesium salts for theprocess and/or product to be within the contemplation of this invention.Generally speaking, all that is necessary is that an overallstoichiometric excess of magnesium oxide be employed in the processesand that the basic magnesium salts be characterized by a metal ratio ofat least 1.1 as long as the other parameters discussed above are met. Infact, it is often advantageous to employ greater amounts of magnesiumoxide than is actually to be incorporated in the basic magnesium saltsto achieve higher metal ratios and/ or shorter reaction periods.

As is apparent, other embodiments of this invention are readily achievedby substituting other acids, diluents, inorganic acidic materials, andalcohol promoters for all or a portion of those used in the foregoingillustrative examples using as a guideline for such substitution thegeneral description of the invention set forth hereinabove.

In the foregoing examples, carbon dioxide, hydrogen sulfide and sulfurdioxide is introduced into the reaction mass as a gas via a submergedinlet line. Obviously other inorganic acidic gases can be introduced ina similar manner. If the acidic material is a liquid organic orinorganic acid, it can be introduced continuously over a specifiedperiod of time, dropwise, in periodic increments, or all at oncedepending on which procedure produces the best results for the specificcombination of inorganic acid, organic acid, acid and promoter.

The order of combining the reactants is not critical although in a givencombination of acids, promoters, and diluents, a particular reactionorder may help achieve optimum results. It should be clear, therefore,that the various components of the reaction mixture can be broughttogether in various combinations e.g., acids and diluent, diluent andpromoters, acids and promoters, magnesium oxide and water, or magnesiumoxide and diluent and these separate combinations mixed together to formthe reaction mixture. It should also be noted that freshly formedmagnesium hydroxide can be substituted for all or a portion of themagnesium oxide used in the processes of this invention. Freshly formedmagnesium hydroxide can be prepared by mixing water and magnesium oxideseparately and adding the magnesium hydroxide thus formed to thereaction mixture. Magnesium hydroxide, like magnesium oxide, has twoequivalents of magnesium per mole.

The basic magnesium salts are primarily useful as additives for fuelsand lubricants and can be employed in the same manner as the known basicsalts of the prior art, for example as described in US. Pats. 2,585,520;2,739,- 124; 2,895,913; 2,889,279; 3,149,074; 3,150,089; and 3,235,494.In lubricants, such as crankcase lubricating oils, the basic magnesiumsalts function as detergents and promote engine cleanliness and reducewear mainly by neutralizing acidic products such as those formed by theoxidation of the oil components or during combustion. The acidicmaterials if not neutralized, lead to increased engine wear and theformation of lacquer on engine parts. The basic magnesium salts disperseinsoluble materials formed in the lubricant as a result of fuelcombustion or oil oxidation thus reducing sludge. The basic magnesiumsalts also reduce or eliminate preignition tendency in gasoline fueledengines relative to, for example, basic cal cium or barium salts whenemployed as lubricant or fuel additives.

When utilized as lubricant additives, the basic magnesium salts will beemployed in amounts such that the magnesium sulfate ash content of thelubricant will vary from about 0.05% to 15% by weight of the totalcomposition depending on the particular application. Thus, in crankcaseoil for most internal combustion engines, the magnesium sulfate ashcontent will vary between 0.1%-5% and usually between 0.1%-2.5%. On theother hand, in marine diesel lubricants where it is customary to employlarge amounts of basic salts, an ash level of up to 15% by weight, oreven more, is not out of the question, although ash levels of 5%l0% aremore frequent. Thus, most lubricant compositions will have a magnesiumsulfate ash content of about 0.1% to about 10% by weight.

However, it is contemplated that the basic salts of this invention maybe used in combination with other conventional additives including othernormal or basic metal salts. Accordingly, the amount of sulfate ashpresent in the lubricant attributable to the basic magnesium salt can bevaried easily by those skilled in the art to obtain the desired overallsulfate ash content.

Other conventional additives which can be used in com bination with thebasic magnesium salts include ashless dispersants of the type disclosedin U.S. Pats. 3,172,892; 3,219,666; 3,381,022; neutral and basic calciumand barium petrosulfonates; corrosion-inhibitors, oxidation inhibitors,antifoam agents, viscosity index improvers, pourpoint depressants, andthe like, such as chlorinated wax, benzyldisulfide, sulfnrized spermoil, sulfurized terpene; phosphorous esters such as trihydrocarbonphosphites; metal thiocarbamates such as zinc dioctyldithiocarbamate;metal phosphorusdithioates such as zinc dioctylphosphorodithioate;polyisobutylene having an average molecular weight of 100,000; etc.

The additives of this invention can be effectively employed in a varietyof lubricating compositions based on diverse oils of lubricatingviscosity such as a natural or synthetic lubricating oil, or suitablemixtures thereof. The lubricating compositions contemplated includeprincipally crankcase lubricating oils for spark-ignited andcompression-ignited internal combustion engines including automobile andtruck engines, two-cycle engine 1u'bricants, av1- ation piston engines,marine and railroad diesel engines, and the like. However, automatictransmission fluids, transaxle lubricants, gear lubricants,metal-working lubr1 cants, hydraulic fluids, and other lubricating oiland grease compositions can benefit from the incorporation of thepresent additives.

Natural oils include animal oils and vegetable o1ls (e.g-, castor oil,lard oil) as well as solvent-refined or ac1d-refined mineral lubricatingoils of the parafiinic, naphthenlc or mixed paraffinic-naphthenic types.Oils of lubricating viscosity derived from coal or shale are also usefulbase oils. Snythetic lubricating oils include hydrocarbon 011s andhalo-substituted hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g. polybutylenes, polypropylenes,propyleneisobutylene copolymers, chlorinated polybutylenes, etc.); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzene, dinonylbenzenes,d1-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, etc.); and the like. Alkylene oxide polymers andinterpolymers and derivatives thereof where the terminal hydroxyl groupshave been modified by esterlfication, etherfication, etc., constituteanother class of known synthetic lubricating oils. These are exemplifiedby the oils prepared through polymerization of ethylene oxide orpropylene oxide, the alkyl and aryl ethers of these polyoxyalkylenepolymers (e.g., methylpolyisopropylene glycol ether having an averagemolecular welght of 1000, diphenyl ether of polyethylene glycol having amolecular weight of 500-1000, diethyl ether of polypro pylene glycolhaving a molecular weight of l000l500, etc.) or monoand polycarboxylicesters thereof, for example, the acetic acid esters, mixed C -C fattyacid esters, or the C oxo acid diester of tetraethylene glycol. Anothersuitable class of synthetic lubricating oils coinprises the esters ofdicarboxylic acids (e.g., phthalic acld, succinic acid, maleic acid,azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid,linoleic acid dimer, etc.) with a variety of alcohols (e.g., butylalcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol,pentaerythritol, etc.). Specific examples of these esters 1ncludedibutyl adipate, di(Z-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, the complex ester formed by reacting one mole ofsebacic acid with two moles of tetraethylene glycol and two moles 'ofZ-ethyl-hexanoic acid, and the like. Silicon-based oils such as thepolyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils andsilicate oils comprise another useful class of synthetic lubricants(e.g., tetraethyl-silicate, tetraisopropyl-silicate,tetra-(Z-ethylhexyl)-silicate, tetra- (4-methyl-2-tetraethyl) silicate,tetra-(p-tert-butylphenyl) silicate, hexyl (4-methyl-2-pentoxy)disiloxane, poly(methyl) siloxanes, poly(methylphenyl)-siloxanes, etc.).Other synthetic lubricating oils include liquid esters ofphosphorus-containing acids (e.g., tricresyl phosphate, trioctylphosphate, diethyl ester of decane phosphonic acid, etc.), polymerictetrahydrofurans, and the like.

When used as fuel additives, the basic magnesium salts will be employedin amounts sufficient to provide magnesium sulfate ash contents of0.000l% to about 1%, usually 0.0001% to 0.5% by weight in petroleumdistillate fuels. When employed in these normally liquid petroleumdistillate fuels, e.g., fuel oils, diesel fuels, gasolines, aviationgasoline, aviation jet fuels, etc., they promote engine cleanliness,particularly of the fuel system such as fuel lines, carburetors,injectors, pumps and the like. In furnace fuel oils, for example, theyserve as antiscreen clogging agents. Furthermore, in diesel fuels andother fuels which tend to produce black exhaust smoke in diesel engines,the basic magnesium salts suppress the formation and evolution of theseblack exhaust smokes in the manner described in German Auslegeschrift1,243,- 915 and 1,273,265 and U.S. Pat. 3,437,465. Likewise, the basicmagnesium salts produced according to the processes of the presentinvention can be employed as vanadium scavengers in furnaces and otherdevices which burn residual fuel oils by introducing the basic magnesiumsalts into the combustion zone in the form of an oil or fuel solution oras an additive in the residual fuel. When used as vanadium scavengers,the basic magnesium salts are advantageously employed in combinationwith particulate aluminum oxide having an average particle size lessthan ten microns.

It is also contemplated that the basic magnesium salts will be employedin fuels in combination with other conventional fuel additives such asde-icers, antiknock agents, other smoke suppressants, and the like. Whenbasic magnesium salts are prepared for use in fuels according to theprocesses of the present invention, it is sometimes desirable to usenon-mineral oil diluents exclusively (e.g., xylene, toluene, heptane,naphtha, or other such diluents as described hereinbefore) and to retainthe basic magnesium salts produced as solutions in these diluents. Ofcourse, combinations of these non-mineral oil diluents and mineral oilcan be used as in the described processes. However, it may be helpful toretain the non-mineral oil diluent in the final product rather thanremove it as is done in the above illustrative examples. The mineraloils are sometimes undesirable in fuels as they lead to the formation ofundesirable carbonaceous deposits on exhaust valves, etc. Moreover, thenon-mineral oil diluents facilitate mixing of the basic magnesium saltsolutions and fuels.

The following are examples of specific lubricants or fuels incorporatingthe basic magnesium salts of this invention. Unless otherwise indicated,percent and parts as used in the specification and claims means percentby weight or parts by weight.

COMPOSITION A SAE 30 mineral lubricating oil containing 0.35% magnesiumsulfate ash as the filtrate of Example 1 and 0.25% calcium sulfate ashas a basic calcium petrosulfonate.

COMPOSITION B SAE l0W-30 mineral lubricating oil containing .9%magnesium sulfate ash as the filtrate of Example 6(B) and 0.06% byweight phosphorus as zinc di-n-octylphosphorodithioate.

COMPOSITION C SAE10 mineral lubricating oil containing 0.75% of theester prepared by reacting in a 1:1 mole ratio polyisobutenyl (averagemolecular weight-1100) substituted succinic anhydride andpentaerythritol, 1.5% magnesium sulfate ash as the filtrate of Example7, 0.075% phosphorus as the adduct of zincdi-cyclohexylphosphorodithioate treated with 0.3 mole of ethylene oxide,2% sulfurized sperm oil having a sulfur content of 10%, 3.5% of a poly-(alkylmethacrylate) viscosity index improver, 0.02% of apoly-(alkylmethacrylate) pour point depressant, and 0.003% of apoly-(alkyl siloxane) antifoam agent.

COMPOSITION D Diesel fuel containing 0.1% magnesium sulfate ash as thefiltrate of Example 6(A).

COMPOSITION E Gasoline containing 0.001% magnesium sulfate ash as thefiltrate of Example 9.

Other specific lubricants and fuels are readily prepared in accordancewith the instructions set forth in the above discussion.

As used in the present specification, all percentages and parts refer topercent by weight and parts by weight unless otherwise indicated.

What is claimed is:

1. The process for preparing oil-soluble basic magnesium saltscomprising intimately contacting at a temperature of about 25 C. up tothe decomposition temperature at least one acidic material with amixture comprising:

(a) At least one member selected from the group consisting ofoil-soluble organic acids and their equivalent derivatives susceptibleto overbasing,

(b) A stoichiometric excess, based on the total equivalents of acid andequivalent derivatives thereof in (a), of basically reacting lightmagnesium oxide,

() Water, there being at least about one-tenth mole of water up to aboutfive moles of water for each mole of magnesium oxide,

(d) At least one lower aliphatic alcohol in an amount such that there isat least about 0.1 mole of alcohol for each mole of water,

(e) At least one substantially inert organic liquid diluent, the diluentbeing present in an amount such that it comprises from about 10% toabout 80% by weight of said mixture,

until reaction between said at least one acidic material and saidmixture substantially ceases, subsequently removing substantially allfree lower aliphatic alcohol, and continuing the contacting of the saidat least one acidic material with said mixture until the liquid phase ofsaid mixture becomes substantially clear and filterable.

2. The process according to claim 1 where the acidic material is aninorganic acidic material.

3. The process according to claim 2 where the acidic material isselected from the class consisting of carbon dioxide, sulfur dioxide,and hydrogen sulfide and (a) is selected from oil-soluble organic acidsand metal salts thereof.

4. The process according to claim 3 where said at least one loweraliphatic alcohol is at least one lower alkanol and the alcohol-watermolar ratio is in the range of about 0.5:1 to about 10:1.

5. The process according to claim 4 where (a) is at least one memberselected from oil-soluble sulfonic and carboxylic acids and their GroupI or Group 11 metal salts.

6. The process according to claim 5 wherein the temperature of saidmixture is maintained at about 50-- 150 C., said diluent comprises fromabout 30% to about 70% by weight of said mixture, said lower alkanol ismethanol or a combination of methanol and at least one other loweralkanol wherein methanol comprises at least about 25% by weight of saidcombination, said alcoholwater ratio is about 0.8:1 to about 3:1, saidinorganic acidic material is carbon dioxide, and wherein the metal ratioof the basic magnesium salts is in excess of about 5.

7. The process according to claim 5 wherein additional light magnesiumoxide and lower alkanol is added to the mixture and the process ofcontacting the mixture with said acidic material is repeated.

8. The process for preparing oil soluble basic magnesium saltscomprising intimately contacting, at a temperature of about C. up to thedecomposition temperature, at least one inorganic acidic material with amixture comprising:

(a) X equivalents of at least one member selected from oil-solubleorganic acids or alkali or alkaline earth metal salts thereof other thanan oil-soluble aliphatic carboxylic acids and alkali and alkaline earthmetal salts thereof,

(b) Y equivalents of at least one member selected from oil-solublealiphatic carboxylic acids and alkali or alkaline earth metal saltsthereof,

wherein the ratio of X:Y is about 1:1 to about 20:1,

(c) Z equivalents of basically reacting magnesium oxide, wherein thevalue of Z X +Y is from about 1.1 to about 30,

(d) At least one lower aliphatic alcohol in an amount such that there isat least about 0.1 mole of alcohol for each mole of water,

(e) Water, there being at least about one-tenth mole of water up toabout five moles of water for each mole of magnesium oxide employed,

(f) A substantially inert organic liquid diluent, said diluentcomprising from about 10% to 80% by weight of said mixture,

until the reaction between said inorganic acidic material and themixture substantially ceases, subsequently removing substantially allfree lower aliphatic alcohol, and continuing the contacting of the saidat least one inorganic acidic material with said mixture until theliquid phase of said mixture becomes substantially clear and filterable.

9. The process according to claim 8 wherein the acidic material isselected from the class consisting of carbon dioxide, sulfur dioxide,and hydrogen sulfide and (a) is selected from oil-soluble organic acidsand metal salts thereof.

10. The process according to claim 9 comprising carbonating at atemperature of about l50 C. a mixture comprising:

(a) X equivalents of at least one member selected from oil-solubleorganic acids or alkali or alkaline earth metal salts thereof other thanan oil-soluble aliphatic carboxylic acids and alkali and alkaline earthmetal salts thereof,

(b) Y equivalents of at least one member selected from oil-solublealiphatic carboxylic acids and alkali or alkaline earth metal saltsthereof,

wherein the ratio of X:Y is about 1:1 to about 10:1,

(c) Z equivalents of basically reacting magnesium oxide, wherein thevalue of Z X Y is from about 1.1 to about 30,

(d) At least one lower aliphatic alcohol in an amount such that there isat least about 0.1 mole of alcohol for each mole of water,

(e) Water, the molar ratio of water to magnesium oxide being from about0.521 to about 30:10 and (f) A substantially inert organic liquiddiluent, said diluent comprising from about 30% to about by weight ofsaid mixture,

until the reaction between carbon dioxide and the mixture substantiallyceases, subsequently removing substantially all free alcohol, andcontinuing carbonation until the liquid phase of said mixture becomessubstantially clear and filterable.

11. The process according to claim wherein the ratio of X:Y is about 1:1to about 10:1, (a) is at least one member selected from oil-solublearomatic carboxylic acids, oil-soluble sulfonic acids, and alkalineearth metal salts thereof and (b) is at least one member selected fromoil-soluble aliphatic carboxylic acids and alkaline earth metal saltsthereof.

:12. The process according to claim 10 wherein the lower aliphaticalcohol is lower alkanol and the molar ratio of alcohol to water isabout 0.5 :1 to about 10:1.

13. The process according to claim 12. wherein lower alkanol is methanolor a combination of methanol and at least one other lower alkanol wheremethanol comprises at least 25% by weight of said combination.

14. The process according to claim 10 wherein additional alcohol andmagnesium oxide is added to the resulting carbonated reaction mixture toform a second reaction mixture, carbonating the second reaction mixtureuntil the reaction between carbon dioxide and said second reactionmixture substantially ceases, subsequently removing substantially allfree alcohol, and continuing carbonation until the liquid phase of saidsecond reaction mixture becomes substantially clear and filterable.

15. The process according to claim 10 wherein (b) comprises at least onemember selected from oleic acid, linoleic acid, isostearic acid, talloil acids and the alkaline earth metal salts of these.

16. The process according to claim 10 wherein the value of is about 2 toabout 12; the lower aliphatic alcohol is methanol or a combination ofmethanol and at least one other lower alkanol wherein methanolconstitutes at least 25% by weight of said combination; and the molarratio of alcohol to water is about 0.8:1 to about 3:1.

17. The process according to claim 10 where said substantially inertorganic liquid diluent comprises mineral oil and at least one additionalsubstantially inert organic liquid medium having a boiling point lowerthan said mineral oil but higher than water.

18. The process comprising contacting at least one inorganic acidicmaterial, selected from the class consisting of carbon dioxide, sulfurdioxide, and hydrogen sulfide, at a temperature of about 25 C. up to thedecomposition temperature with a mixture comprising (a) M equivalents ofat least one member selected from oil-soluble hydroxy-substitutedaromatic carboxylic acids or equivalent derivatives thereof susceptibleto overbasing,

(b) N equivalents of at least one member selected from oil-solublesulfonic acids and equivalent derivatives thereof susceptible tooverbasing,

(c) Q equivalents of basically reacting light magnesium oxide where theratio of M:N is about 1:1 to about 20:1 and the value of is from about1.1 to about 30,

(d) Water, there being at least about one-tenth mole of water up toabout five moles of water for each mole of magnesium oxide, and

(e) A substantially inert organic liquid diluent, the

diluent being present in an amount such that it comprises from about 10%to about 80% by Weight of said mixture,

until the reaction between the inorganic acidic material and the mixturesubstantially ceases.

19. The process according to claim 18 comprising carbonating a mixturecomprising:

(a) M equivalents of at least one member selected from oil-solublehydroxy-substituted aromatic car- 30 boxylic acids or equivalentderivatives thereof susceptible to overbasing,

(b) N equivalents of at least one member selected from oil-solublesulfonic acids and equivalent derivatives thereof susceptible tooverbasing,

(c) Q equivalents of basically reacting magnesium oxide where the ratioof M:N is about 1:1 to about 20:1 and the value of Q M +N is from about1.1 to about 30,

(d) Water, the molar ratio of water to magnesium being from about0.52110 to about 3.0:1.0, and

(e) A substantially inert organic liquid diluent, the

diluent being present in an amount such that it comprises from about 30%to about 70% by weight until the reaction between the carbon dioxide andthe mixture substantially ceases.

20. A process for preparing oil-soluble basic magnesium salts comprisingcarbonating at a temperature of about 50150 C. a mixture comprising:

(a) M equivalents of at least one member selected from oil-solublehydroxy-substit-uted aromatic carboxylic acids and their alkali oralkaline earth metal salts,

(b) N equivalents of at least one member selected from oil-solublesulfonic acids and their alkali or alkaline earth metal salts,

(c) Q equivalents of basically reacting magnesium oxide where the ratioof M :N is about 1:1 to about 20:1 and the value of is from about 2 toabout 12,

(d) Water, the molar ratio of water to magnesium being from about 0.5:1.0 to about 3.0:1.0, and at least one lower aliphatic alcohol in anamount such that the molar ratio of alcohol to water in said mixture isin the range of about 0.5 :1 to 10:1,

(e) A substantially inert organic liquid diluent, the diluent beingpresent in an amount such that it comprises from about 30% to about 70%by weight of said mixture,

until the reaction between the carbon dioxide and the mixturesubstantially ceases, subsequently removing substantially all freealcohol, and continuing carbonation until the liquid phase of saidmixture becomes substantially clear and filterable.

21. A process according to claim 20 wherein the lower aliphatic alcoholis methanol or a combination of meth anol and at least one other loweralkanol wherein methanol constitutes at least 25 by weight of saidcombination and wherein the molar ratio alcohol to water is about 0.8 toabout 3:1.

22. The process according to claim 20 wherein (a) is at least one memberselected from oil-soluble aliphatic hydrocarbon-substituted salicylicacids and the alkali or alkaline earth metal salts thereof, wherein eachaliphatic hydrocarbon substituent contains an average of at least aboutsixteen carbon atoms per substituent and there are one to threesubstituents per molecule of salicyclic acid or alkali or alkaline earthmetal salt thereof.

23. The process according to claim 20 wherein additional alcohol andmagnesium oxide is added to the resulting carbonated reaction mixture toform a second reaction mixture, carbonating the second reaction mixtureuntil reaction between carbon dioxide and said second reaction mixturesubstantially ceases, subsequently removing substantially all freealcohol, and continuing carbonation until the liquid phase of saidsecond reaction mixture becomes substantially clear and filterable.

24. An oil-soluble composition produced according to the process ofclaim 1.

25. An oil-soluble composition produced according to the process ofclaim 5.

26. An oil-soluble composition produced according to the process ofclaim 8.

27. An oil-soluble composition produced according to the process ofclaim 10.

28. An oil-soluble composition produced according to the process ofclaim 14.

29. An oil-soluble composition produced according to the process ofclaim 16.

30. An oil-soluble composition produced according to the process ofclaim 17.

31. An oil-soluble composition produced according to the process ofclaim 18.

32. An oil-soluble composition produced according to the process ofclaim 20.

33. An oil-soluble composition produced according to the process ofclaim 21.

34. An oil-soluble composition produced according to the process ofclaim 23.

35. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 24.

36. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 25.

37. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 26.

38. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 27.

39. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 28.

40. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 29.

41. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 30.

42. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 31.

43. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 32.

44. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 33.

45. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 34.

46. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 35.

47. A lubricant or fuel comprising, respectively, a major amount of alubricating oil or a normally liquid petroleum distillate fuel and adetergent amount of a composition according to claim 36.

48. A lubricant comprising a major amount of a mineral lubricating oiland a detergent amount of a composition according to claim 27.

49. A lubricant comprising a major amount of a mineral lubricating oiland a detergent amount of a composition according to claim 29.

50. A lubricant comprising a major amount of a mineral lubricating oiland a detergent amount of a composition according to claim 32.

References Cited UNITED STATES PATENTS 2,616,904 11/1952 Asself et al.25233 3,027,325 3/1962 McMillen et al. 25233 3,057,896 l0/1962 Schlichtet al. 25233 DANIEL E. WYMAN, Primary Examiner I. VAUGHN, AssistantExaminer US. Cl. X.R.

44 s1, 57, 66, 7o, 76; 2s2 32.s, 32.7 E, 32.7 HC, 33.2, 39

